Fragrance composition

ABSTRACT

A combination of a musk with one or more ingredients of specific chemical structures in particular proportions makes it possible to obtain a fragrance composition which can mask an odor peculiar to an acidic hair cosmetic composition and is also excellent in long-term stability. By combining fragrant materials selected as desired from (E) ingredients each characterized primarily by the abundant release of a scent from foam, (F) ingredients each characterized primarily by the abundant release of a scent from a bottle mouth and (G) ingredients each characterized by good persistence of scent, an excellent fragrance composition can be obtained with a good balance among the abundant release of a scent from foam, the abundant release of a scent from a bottle mouth, and good persistence of scent.

FIELD OF THE INVENTION

This invention relates to fragrance compositions which exhibit a highmasking effect on acid smell, retain good long-term stability at hightemperatures, give off a good scent from a bottle in which the haircosmetic composition is filled as well as a good scent upon applicationof the hair cosmetic composition and are excellent in the persistence ofsuch scent after the application, even when added to a hair cosmeticcomposition having a pH of 1 to 5.

BACKGROUND OF THE INVENTION

Conventional hair cosmetic compositions generally have a pH in theneutral range and contain little acid therein, so no problem has beenmanifested about an acid smell from a cosmetic base. Further, noattention has been paid to fragrances added to hair cosmeticpreparations or their stability in the acidic range.

With the consumers' needs changing in recent years, developments havebeen made to formulate hair cosmetic compositions having a pH in theacidic range such that various functions can be imparted to them. Acidichair cosmetic compositions, however, give off apeculiar acid smell.Aneed has, therefore, arisen to mask a smell of a cosmetic basecontained in acidic hair cosmetic compositions.

Acidic hair cosmetic compositions are low in pH. When fragrances addedto conventional hair cosmetic compositions are simply added to suchacidic hair cosmetic compositions, they develop such a problem that anodor balance deteriorates and an unpleasant odor manifests(JP-A-2000-143453).

The present invention provides a fragrance composition which can mask asmell peculiar to an acidic hair cosmetic composition and is alsoexcellent in long-term stability. The present invention also provides afragrance composition which gives off a good scent from a bottle inwhich a hair cosmetic composition is filled, as well as a good scentupon application of the hair cosmetic composition, and is excellent inthe persistence of such scent after the application.

DISCLOSURE OF THE INVENTION

The present inventors, therefore, have proceeded with variousinvestigations. As a result, it has been found that a combination of amusk with one or more ingredients of specific chemical structures inparticular proportions makes it possible to obtain a fragrancecomposition which can mask a smell peculiar to an acidic hair cosmeticcomposition and is also excellent in long-term stability.

Described specifically, the present invention provides a fragrancecomposition to be added to a hair cosmetic composition having a pH of 1to 5, comprising the following ingredients (A) and (B), or (A) and (C),or (A), (B) and (C):

(A) from 0.1 to 70 wt. % of a musk;

(B) from 0.001 to 80 wt. % of at least one compound selected from thefollowing compounds (i) to (v):

-   -   (i) compounds represented by the following formula (1):        R¹—COOR²  (1)        wherein R¹ represents a linear, branched or cyclic hydrocarbon        group having from 2 to 14 carbon atoms, which may contain an        oxygen atom or nitrogen atom in at least one carbon-to-carbon        bond thereof, and R² represents a linear, branched or cyclic        hydrocarbon group having from 1 to 15 carbon atoms, which may        contain an oxygen atom or nitrogen atom in at least one        carbon-to-carbon bond thereof,    -   (ii) compounds represented by the following formula (2):        R³—COOR⁴  (2)        wherein R³ represents a hydrogen atom or methyl group, and        R⁴represents a hydrocarbon group or cyclic hydrocarbon group, in        which an α-carbon or β-carbon to an ether linkage in an ester        group in formula (2) has a branched chain,    -   (iii) lactones having total carbon numbers of from 5 to 14,    -   (iv) ketone compounds having a cyclic or chain skeleton and        having total carbon numbers of from 5 to 14,    -   (v) aldehydes having total carbon numbers of from 5 to 14; and

(C) from 0.01 to 90 wt. % of a hydrocarbon having a total carbon numberof from 5 to 15.

Further, the present invention also provides a hair cosmetic compositionhaving a pH of 1 to 5, comprising the above-described fragrancecomposition.

For a fragrance composition to be added to an acidic hair cosmeticcomposition having a pH of 1 to 5, on the other hand, it is important asbasic requirements to mask an acid smell derived from a cosmetic baseand to have good long-term storage stability. Further, from theviewpoint of its comfortable use by consumers and the enhancement of itsattraction as merchandise, it is also important that the hair cosmeticcomposition has a good scent at each of the following three stages:

-   -   b 1. The scent emitted from the bottle mouth is favorable since        this serves as one of the important factors for consumers upon        selecting a brand at the stores.    -   2. The scent upon its application is favorable.    -   3. A favorable scent remains at an adequate intensity on the        hair after the application.

The present invention also provides a fragrance composition for a haircosmetic composition having a pH of 1 to 5, comprising at least twoingredients selected from the following ingredients (E), (F) and (G),wherein the content of ingredient (E) is from 10 wt. % to 70 wt. % ofthe fragrance composition, the content of ingredient (F) is from 5 wt. %to 60 wt. % of the fragrance composition, and the content of ingredient(G) is from 10 wt. % to 60 wt. % of the fragrance composition:

(E) α-amylcynnamic aldehyde, acetophenone, decanal, undecanal,undecenal, dodecanal, 2-methylundecanal, octanal, nonanal,allylcyclohexyl propionate, allyl phenoxyacetate, anisaldehyde, anisylacetate, anisyl acetone, borneol, 3-(p-tert-butylphenyl)-propanal(“BOURGENAL”, trade name of Quest International B.V..),7-methyl-3,5-dihydro-2H-benzodioxepin-3-one (“CALONE”, trade name ofPfizer Inc.), cinnamyl acetate, cis-4-decenal, cis-jasmone,citronellyloxy acetaldehyde, dodecanenitrile (“CLONAL”, trade name ofInternational Flavors & Fragrances Inc.),2-methyl-3-(isopropylphenyl)-propanal (cyclamen aldehyde),dihydrojasmone, methyl dihydrojasmonate, dihydromircenol,tricyclodecylidene-4-butanal (“DUPICAL”, trade name of QuestInternational B.V..), ethyl 2-cyclohexylpropionate (“ETHYL POIRENATE”,trade name of Kao Corporation), ethyl2,6,6-trimethyl-1,3-cyclohexadiene-1-carboxylate (“ETHYL SUFRANATE”,trade name of Quest International B.V..), ethyl isovalerate, ethyllinalol, ethyl vanillin, eugenol,6-ethylidenoctahydro-5,8-methano-2H-1-benzopyran-2-one (“FLOREX”, tradename of Firmenich, Inc.), ethyl tricyclodecan-2-yl-carboxylate(“FRUITATE”, trade name of Kao Corporation), franeol,ethyl-3-(bicyclo[2.2.1]hepto-5-en-2-yl)-3-methyl glycidate (“GLYCOMEL”,trade name of Firmenich, Inc.),2-methyl-3-(3,4-methylenedioxyphenyl)-propanol (“HELIONAL”, trade nameof International Flavors & Fragrances Inc.), cis-3-hexenylmethylcarbonate (“LIFFAROME”, trade name of International Flavors &Fragrances Inc.), 2-methyl-3-(4-tert-butylphenyl)-propanal (“LILIAL”,Givaudan-Roure Corporation),4(3)-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxald ehyde(“LYRAL”, trade name of International Flavors & Fragrances Inc.), methylanthranilate, methyl β-naphthyl ketone,4(3)-(4-methyl-3-pentenyl)-3-cyclohexene-1-carboxaldehyde (“MYRACALDEHYDE”, trade name of International Flavors & Fragrances Inc.),2-(2-(4-methyl-3-cyclohexen-1-yl)propyl)cyclopentanone (“NECTARYL”,trade mark of Givaudan-Roure Corporation), nookkatone,phenylacetaldehyde, 2-cyclohexylpropanal (“POLLENAL II”, trade name ofKao Corporation), 8-methoxytricyclodecane-4-carboxaldehyde (“SCENTENAL”,trade name of Firmenich, Inc.), thymol, trans-2-decenal,trans-2-hexanal, tricyclodecenyl acetate, tricyclodecenyl propionate,and 1-acetyl-2,6,10-trimethylcyclododeca-2,5,9-triene (“TRIMOFIX”, tradename of International Flavors & Fragrances Inc.),

(F) 1-octen-3-yl acetate, 2,5-decadienal, 2,4-octadienal,2,6-nonadienal, 1,3-oxathiane 2-methyl-4-propionate, 2-methylbutyl2-methylbutyrate, 2-methylbutyl isovalerate, 2-methylbutyl valerate,acetophenone, acetylcedrene [ethanone,1-(2,3,4,7,8,8a-hexahydro-3,6,8,8-tetramethyl-1H-3a, 7-methanoazulen-5-yl)-]β-methylnaphthyl ketone, α-damascon, hexanol, hexanal,heptanal, allylionone, allyl heptanoate, allyl hexanoate, α-pinene,α-terpinene, β-damascon, benzaldehyde, benzyl acetate, benzylpropionate, camphor, 2-methyl-3-(para-methoxyphenyl)-propylaldehyde(“CANTHOXAL”, trade name of International Flavors & Fragrances Inc.),cedrene, 3-propylbicyclo(2.2.1)hept-5-ene-2-carbaldehyde (“CHRYSANTHAL”,trade name of Quest International B.V.), cinnamic alcohol,cis-3-hexenol, cis-3-hexenyl propionate, cis-jasmone, citral,citronellal, citronellol, citronellyl nitrile, thiol-added orsubstituted products of limonene (for example, “CORPS PAMPLEMOUSSE”,trade name of Prodasynth S.A.), methyl cyclopentylidenacetate,dimethlbenzylcarbinyl acetate,1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-2-buten-1-one (“DAMASCENONE”,trade name of Firmenich, Inc.),1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-2-buten-1-one (“DELTA-DAMASCONE”,trade name of International Flavors & Fragrances Inc.), dihydrojasmone,ethylmaltol, ethyl trimethylhexanoate, ethyl 2-methylbutylate, ethylbutyrate, ethyl heptanoate, ethyl hexanoate, ethyl nonanoate, ethyloctanoate, ethyl propionate, ethyl valerate, fenchone,p-ethyl-2,2-dimethylhydrocinnamaldehyde (“FLORALOZONE”, trade name ofInternational Flavors & Fragrances Inc.), ethyl2-tert-butylcyclohexylcarbonate (“FLORAMAT”, trade name of KaoCorporation), 2-sec-butylcyclohexanone (“FRESCOMENTHE”, trade name ofGivaudan-Roure Corporation), ethyl-2-methyl-1,3-dioxolan-2-acetate,geraniol, geranyl nitrile, 3-methyl-5-prop-2-cyclohexen-1-one(“GRAVENONE”, trade name of Dragoco, Inc.), hexylcinnamic aldehyde,heptyl cyclopentanone, iron, isobutyl salicylate,1-(2,4,4-trimethyl-2-cyclohexen-1-yl)-2-buten-1-one (“ISO-DAMASCONE”,trade name of Dragoco, Inc.), L-carvone,3,7-dimethyl-2(3),6-nonadienenitrile (“LEMONILE”, trade name ofGivaudan-Roure Corporation), limonene, L-menthol, menthone, maltol,3-methyl-5-phenylpentanal (“MEFRANAL”, trade name of Quest InternationalB.V..), methyl dihydrojasmonate, methyl benzoate, methyl butyrate,methyl geranylate, methyl octanoate, methyl salicylate, methyl valerate,butyl butyrate, hexyl acetate, hexylcyclopentanone, amyl valerate, amylbutyrate, amyl propionate, orthomethoxycinnamic aldehyde,o-tert-butylcyclohexyl acetate, para-amylcyclohexanone, paracymene,phenylethyl alcohol, phenylethylpropionate, phenylhexanol, phenylpropylacetate, 4-methyltricyclo[6.2.1.02.7]undecan-5-one (“PLICATONE”, tradename of Firmenich, Inc.), p-menthane-8-thiol-3-one,p-tert-butylcyclohexyl acetate, styrallyl acetate, terpineol,terpinolene, terpinyl propionate, trans-2-hexanal, trans-2-hexenylacetate, trimethylhexanal, 2,4-dimethyl-3-cyclohexenylcarboxaldehyde(“TRIPLAL”, trade name of International Flavors & Fragrances Inc.),2,2,5-trimethyl-5-pentylcyclopentanone (“VELOUTONE”, trade name ofFirmenich, Inc.), and 4-cyclohexyl-4-methyl-2-pentanone (“VETIVERTONE”,trade name of Quest International B.V..), and

(G) allyl anthranillate, 1-(2-tert-butylcyclohexyloxy)-2-butanol (“AMBERCORE”, trade name of Kao Corporation), 7-cyclohexadecenolide(ambrettolide), (3α,6,6,9α-tetramethyldodecahydronaphtho[2.1-b]furan(“AMBROXANE”, trade name of Kao Corporation),2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol (“BACDANOL”,trade name of International Flavors & Fragrances Inc.; “BANGALOL”, tradename of Givaudan-Roure Corporation), benzophenone, benzyl alcohol,caryophyllene, 6,7-dihydro-1,1,2,3,3,-pentamethyl-4(5H)-indanone(“CASHMERAN”, trade name of International Flavors & Fragrances Inc.),4-acetyl-6-tert-butyl-1,1-dimethylindan (“CELESTOLIDE”, trade name ofInternational Flavors & Fragrances Inc.), cis-3-hexenyl anthranylate,4-hexenyl salicylate, coumarin, cyclopentadecanone, dynascone,3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten-2-ol (“EVANOL”,trade name of Givaudan-Roure Corporation), ethyl salicylate, eugenolacetate, geranyl cyclopentanone, oxacyclohexadecen-2-one (“HABANOLIDE”,trade name of Firmenich, Inc.), heliotropine, heliotropyl acetone,hexadecanolide, α-ionone, β-ionone,7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethylnap hthalene (“ISOE SUPER”, trade name of International Flavors & Fragrances Inc.),isobutyl anthranylate, isoeugenol acetate, δ-decalactone,α-methylionone, γ-methylionone, 3-methylcyclopentadecenone (“MUSCENONEDELTA”, trade name of Firmenich, Inc.), 3-methylcyclopentadecanone(muscone), ethylene dodecanedioate (“MUSK C-14”, trade name of TakasagoInternational Corporation), musk ketone, 11-oxa-16-hexadecanolide (“MUSKR-1”, trade name of Quest International B.V.), 5-cyclohexadecen-1-one(“MUSK TM-II”, trade name of Soda Aromatic Co., Ltd.), butylanthranylate, hexyl salicylate, amyl salicylate,10-oxa-16-hexadecanolide (“OXALIDE”, trade name of TakasagoInternational Corporation),4,6,6,7,8,8-hexamethyl-1,3,4,6,7,8-hexahydrocyclopentaben zopyran(“PEARLIDE PURE”, trade name of Kao Corporation),6-acetyl-1,1,2,4,4,7-hexatetralin (“TONALIDE”, tradenameof PFW AromaChemicals B.V.), cis-8-cyclohexadecenolide (“SCENTOLIDE”, trade name ofSynarom, Inc.),3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-pentan-2-ol(“SANDALORE”, trade name of Givaudan-Roure Corporation),2-methyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol(“SANDALMYSORE CORE”, trade name of Kao Corporation),4-(parahydroxyphenyl)-2-butanone (“RASPBERRY KETONE”, trade name ofTakasago International Corporation),3,3-dimethyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-pen ten-2-ol(“POLYSANTOL”, trade name of Firmenich, Inc.),2-cyclohexylidene-2-phenyl acetonitrile (“PEONILE”, trade name ofGivaudan-Roure Corporation), and cyclopentadecanolide (“PENTALIDE”,trade name of Soda Aromatic Co., Ltd.).

DETAILED DESCRIPTION OF THE INVENTION

As the musk employed as ingredient (A) in the fragrance compositionaccording to the present invention, a synthetic musk can be mentioned.Specific examples include muscone, civetone, cyclopentadecanone,5-cyclohexadecen-1-one, cyclopentadecanolide, ambrettolide,12-ketocyclopentadecanolide, cyclohexadecanolide, 7-cyclohexadecanolide,12-oxa-16-hexadecanolide, 11-oxa-16-hexadecanolide,10-oxa-16-hexadecanolide, ethylene brassylate, 3-methycyclopentadecenone(muscenone, NF), cyclopentadenolide (pentalide), ethylenedodecanedioate,musk ketone, 6-acetylhexamethylindan (“PHANTOLID”, trade name of PFWAroma Chemicals B.V.), 4-acetyldimethyl-t-butylindan (“CELESTOLIDE”,trade name of International Flavors & Fragrances Inc.),5-acetyltetramethylisopropylindan (“TRASEOLIDE”, trade name of QuestInternational B.V.), 6-acetylhexatetralin (“TENTAROME”, trade name ofPFW Aroma Chemicals B.V.),tetramethyl-6-ethyl-7-acetyl-tetrahydronaphthalene (“VERSALIDE”, tradename of Givaudan-Roure Corporation), formylethyltetramethyltetralin,acetyldimethyltetrahydrobenzindanone (“VITALIDE”, trade name of TakasagoInternational Corporation), hexamethylhexahydrocyclopentabenzopyran(“GALAXOLIDE”, trade name of International Flavors & Fragrances Inc.),and 3-methylcyclopentadeceone (“MUSCENONE DELTA”, Firmenich, Inc.).Among these synthetic musks, preferred examples are muscone,ambrettolide, ethylene brassylate, musk ketone,3-methylcyclopentadecenone (muscenone, NF), cyclopentadecenolide(pentalide), hexamethylhexahydrocyclopentabenzopyran (“GALAXOLIDE”,trade name of International Flavors & Fragrances Inc.), and3-methylcyclopentadeceone (“MUSCENONE DELTA”, Firmenich, Inc.).

From the viewpoint of including an amount sufficient to mask an acidsmell, ensuring a harmony in fragrance with other materials andimparting mildness to fragrance, the content of the musk is from 0.1 to70 wt. %, preferably from 1 to 50 wt. %, morepreferablyfrom2 to 40 wt. %of the fragrance composition.

Ingredient (B) employed in the present invention consists of one or morecompounds selected from the above-described compounds (i) to (v),although a combination of two or more compounds is preferred.

In ingredient (B)(i) of formula (1), the groups represented by R¹ and R²can each be a linear, branched or cyclic hydrocarbon group, or a groupcontaining a linear, branched or cyclic hydrocarbon group with an oxygenatom or nitrogen atom inserted in at least one carbon-to-carbon bondthereof. It is to be noted that the term “hydrocarbon group” as usedherein includes both saturated and unsaturated ones and the term “cyclichydrocarbon group” as used herein includes saturated, unsaturated andaromatic, cyclic hydrocarbon groups. As the atom inserted in the atleast one carbon-to-carbon bond, an oxygen atom or a nitrogen atom canbe mentioned, with an oxygen atom being preferred. A preferred form oflinkage with an oxygen atom contained therein is an ether linkage in alinear ether or cyclic ether. R¹ has from 2 to 14 carbon atoms, while R²has from 1 to 15 carbon atoms.

Preferred examples of R¹ and R² include alkyl groups, alkenyl groups,cyclic hydrocarbon groups, cyclic hydrocarbyl-alkyl groups,cyclichydrocarbyl-alkenyl groups, aromatic hydrocarbon groups, aromatichydrocarbyl-alkyl groups, aromatic hydrocarbyl-alkenyl groups, andmonoterpene and other terpene groups.

Examples of the compound of formula (1) include terpenyl esters,aliphatic esters, and aromatic esters. Illustrative of the terpenylesters of formula (1) are citronellyl propionate, geranyl propionate,linalyl propionate, terpinyl propionate, rhodinyl propionate, nerylpropionate, carbinyl propionate, menthyl propionate, bornyl propionate,isobornyl propionate, linalyl butyrate, geranyl butyrate, citronellylbutyrate, rhodinyl butyrate, neryl butyrate, terpenyl butyrate, santalylbutyrate, citronellyl isobutyrate, geranyl isobutyrate, linalylisobutyrate, rhodinyl isobutyrate, neryl isobutyrate, terpinylisobutyrate, linalyl isovalerate, citronellyl isovalerate, geranylisovalerate, menthyl isovalerate, terpinyl isovalerate, linalylhexanoate, citronellyl hexanoate, geranyl hexanoate, linalyl octanoate,citronellyl tiglate, geranyl benzoate, linalyl benzoate, geranylphenylacetate, citronellyl phenylacetate, rhodinyl phenylacetate,menthyl phenylacetate, linalyl cinnamate, citronellyl tiglate, geranyltiglate, methyl geranate, ethyl geranate, methyl cyclogeranate, ethylcyclogeranate, and ethylcitronellyl oxalate.

Examples of the aliphatic esters of formula (1) include ethylpropionate, propyl propionate, allyl propionate, butyl propionate,isobutyl propionate, isoamyl propionate, hexyl propionate, cis-3-hexenylpropionate, trans-2-hexenyl propionate, decenyl propionate,tricyclodecenyl propionate, methyl butyrate, ethyl butyrate, propylbutyrate, isopropyl butyrate, allyl butyrate, butyl butyrate, isobutylbutyrate, amyl butyrate, isoamyl butyrate, hexyl butyrate, heptylbutyrate, cis-3-hexenyl butyrate, trans-2-hexenyl butyrate, octylbutyrate, propylene glycol dibutyrate, cyclohexyl butyrate,tetrahydrofurfuryl butyrate, methyl isobutyrate, ethyl isobutyrate,propyl isobutyrate, isopropyl isobutyrate, butyl isobutyrate, isobutylisobutyrate, isoamyl isobutyrate, hexylisobutyrate,cis-3-hexenylisobutyrate, 2,4-hexadienyl isobutyrate,1,3-dimethyl-3-butenyl isobutyrate, octyl isobutyrate, tricyclodecenylisobutyrate, methyl 2-methylbutyrate, ethyl 2-methylbutyrate,2-methylbutyl 2-methylbutyrate, hexyl 2-metylbutyrate, cis-3-hexenyl2-methylbutyrate, allyl 2-ethylbutyrate, ethyl 3-hydroxybutyrate, methylvalerate, ethyl valerate, propyl valerate, butyl valerate, isobutylvalerate, amyl valerate, cis-3-hexenyl valerate, methyl isovalerate,ethyl isovalerate, propyl isovalerate, isopropyl isovalerate, allylisovalerate, butyl isovalerate, isobutyl isovalerate, isoamylisovalerate, 2-methylbutyl isovalerate, hexyl isovalerate, heptylisovalerate, ethyl tricyclo[5.2.1.0^(2,6)]decan-2-yl carboxylate(“FRUITATE”, Kao Corporation), and ethyl 2-cyclohexylpropionate(“POIRENATE”, Kao Corporation). Preferred are butyl propionate, ethylbutyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, isobutylbutyrate, amyl butyrate, isoamyl butyrate, cis-3-hexenyl butyrate, ethylisobutyrate, butyl isobutyrate, isobutyl isobutyrate, ethyl2-methylbutyrate, 2-methylbutyl 2-methylbutyrate, ethyl valerate, butylvalerate, isobutyl valerate, amyl valerate, ethyl isovalerate, butylisovalerate, isobutyl isovalerate, isoamyl isovalerate, 2-methylbutylisovalerate, ethyl tricyclo[5.2.1.0^(2,6)]decan-2-yl carboxylate(“FRUITATE”, Kao Corporation), and ethyl 2-cyclohexylpropionate(“POIRENATE”, Kao Corporation).

Examples of the aromatic esters of formula (1) include ethylbenzylacetoacetate, benzyl propionate, styralyl propionate, anisylpropionate, phenylethyl propionate, cinnamyl propionate, phenylpropylpropionate, dimethylbenzylcarvinyl propionate, phenoxyethyl propionate,propylene glycol dipropionate, ethyl 3-hydroxy-3-phenylpropionate,isobutyl furanpropionate, benzyl butyrate, cinnamyl butyrate,phenylethyl butyrate, dimethylbenzylcarvinyl butyrate, benzylisobutyrate, p-cresyl isobutyrate, cinnamyl isobutyrate, phenylethylisobutyrate, phenoxyethyl isobutyrate, phenylpropyl isobutyrate,styrallyl isobutyrate, dimethylbenzylcarvinyl isobutyrate,dimethylpheylethylcarvinyl isobutyrate, decahydro-β-naphthylisobutyrate, benzyl 2-methylbutyrate, phenylethyl 2-methylbutyrate,benzyl valerate, phenylethyl valerate, furfuryl valerate, benzylisobutyrate, cinnamyl isovalerate, phenylethyl isovalerate, phenylpropylisovalerate, benzyl hexanoate, benzyl octanoate, phenylethyl octanoate,p-cresyl octanoate, phenylethyl nonaoate, benzyl dodecanoate (benzyllaurate), methyl benzoate, ethyl benzoate, propyl benzoate, isopropylbenzoate, allyl benzoate, isobutyl benzoate, isoamyl benzoate, prenylbenzoate, hexyl benzoate, cis-3-hexenyl benzoate, benzyl benzoate,phenylethyl benzoate, ethyl o-methoxybenzoate, methyldihydroxydimethylbenzoate, methyl phenylacetate, ethyl phenylacetate,propyl phenylacetate, isopropyl phenylacetate, butyl phenylacetate,isobutyl phenylacetate, isoamyl phenylacetate, hexyl phenylacetate,cis-3-hexenyl phenylacetate, benzyl phenylacetate, phenylethylphenylacetate, p-cresyl phenylacetate, eugenyl phenylacetate, isoeugenylphenylacetate, methyl cinnamate, ethyl cinnamate, propylcinnamate,isopropyl cinnamate, allyl cinnamate, isobutyl cinnamate, isoamylcinnamate, benzyl cinnamate, cinnamyl cinnamate, phenylethyl cinnamate,dimethyl phthalate, diethyl phthalate, methyl salicylate, ethylsalicylate, butyl salicylate, isobutyl salicylate, amyl salicylate,isoamyl salicylate, allyl salicylate, hexyl salicylate, cis-3-hexenylsalicylate, cyclohexyl salicylate, phenyl salicylate, benzylsalicylate,phenylethyl salicylate, p-cresyl salicylate, allyl phenoxyacetate, ethylphenylpropionate, benzyl tiglate, phenylethyl tiglate, cinnamyl tiglate,benzyl angelate, phenylethyl angelate, cinnamyl angelate, and phenylangelate.

Preferred are benzyl isovalerate, cinnamyl isovalerate, phenylethylisovalerate, ethyl benzoate, propyl benzoate, isopropyl benzoate, allylbenzoate, isobutyl benzoate, isoamyl benzoate, prenyl benzoate, hexylbenzoate, cis-3-hexenyl benzoate, benzyl benzoate, phenylethyl benzoate,methyl cinnamate, ethyl cinnamate, methyl salicylate, ethyl salicylate,amyl salicylate, isoamyl salicylate, hexyl salicylate, and cis-3-hexenylsalicylate.

The content of ingredient (B)(i) is from 0.001 to 80 wt. %, preferablyfrom 1 to 80 wt. %, more preferably from 1.5 to 60 wt. % of thefragrance composition.

In ingredient (B) (ii) of formula (2), the hydrocarbon group or thecyclic hydrocarbon group represented by R⁴, in which an α-carbon orβ-carbon to an ether linkage in an ester group in formula (2) has abranched chain, can be a group represented by the following formula (2a)or (2b):

wherein R⁵ represents a hydrogen atom or an alkyl or alkenyl grouphaving from 1 to 14 carbon atoms or forms an unsaturated bond with acarbon atom in R⁶ or R⁷, R⁶ and R⁷ each represents an alkyl or alkenylgroup having 1 to 14 carbon atoms or R⁵ and R⁶ are fused together toform a saturated or unsaturated, cyclic hydrocarbon group having 4 to 8carbon atoms, said cyclic hydrocarbon group being optionally substitutedby one or more alkyl or alkenyl groups.

Examples of the compound of formula (2) include terpenyl esters offormic acid and acetic acid, fatty esters of formic acid and aceticacid, and aromatic esters of formic acid and acetic acid. Illustrativeof the terpenyl esters of formic acid and acetic acid are linalylformate, citronellyl formate, geranyl formate, neryl formate, rhodinylformate, terpinyl formate, cedryl formate, caryophyllene formate,ocimenyl acetate, citronellyl acetate, lavandulyl acetate,isodihydrolavandulyl acetate, nerolidol acetate, geranyl acetate,linalyl acetate, myrcenyl acetate, dihydromyrcenyl acetate, rhodinylacetate, neryl acetate, tetrahydromugol acetate, ethyllinalyl acetate,carvyl acetate, dihydrocarvyl acetate, dihydrocuminyl acetate, terpinylacetate, dihydrocarbinyl acetate, isopregol acetate, menthyl acetate,dihydroterpinyl acetate (menthanyl acetate), citryl acetate, myrcenylacetate, nopyl acetate, penchyl acetate, n-bornyl acetate, isobornylacetate, guaiyl acetate, cedryl acetate, verbenyl acetate, caryophylleneacetate, santalyl acetate, vetiveryl acetate, and guaiac acetate.Preferred is linalyl acetate.

Examples of the aliphatic esters of formic acid and acetic acid include“APHERMATE” (trade name of International Flavors & Fragrances Inc.),oxyoctaline formate, isopropyl acetate, isobutyl acetate, 3-octylacetate, cyclohexyl acetate, p-t-butylcyclohexyl acetate,2,4-dimethyl-3-cyclohexenylmethyl acetate, α,3,3,-trimethylcyclohexanemethyl acetate (“ROSAMUSK”, trade name ofInternational Flavors & Fragrances Inc.), o-t-butylcyclohexyl acetate,1-ethylcyclohexyl acetate, tricyclodecenyl acetate,2,4-dimethyl-cyclohexen-1-methanyl acetate (“FLORALATE”, trade name ofInternational Flavors & Fragrances Inc.), decahydro-β-naphthyl acetate,1-acetoxy-2-sec-butyl-1-vinylcyclohexane, tricyclodecyl acetate,tetrahydrofurfuryl acetate, 3-pentyltetrahydropyranyl acetate (“JASMAL”,trade name of International Flavors & Fragrances Inc.),5-methyl-3-butyltetrahydropyranyl acetate (“JASMELIA”, trade name ofInternational Flavors & Fragrances Inc.), ethyl acetoacetate, ethyl2-hexylacetoacetate, methyl cyclopentylidenacetate, allylcyclohexylacetate, isopropyl cyclohexenylacetate, ando-t-butylcyclohexyl acetate. Preferred are tricyclodecenyl acetate ando-t-butylcyclohexyl acetate.

Examples of the aromatic esters of formic acid and acetic acid includebenzyl formate, methylphenylcarbinyl acetate, styralyl acetate,p-methylbenzyl acetate, anisyl acetate, piperonyl acetate, acetylvanillin, rosephenone, hydratropyl acetate, 2,4-dimethylbenzyl acetate,cuminyl acetate, dimethylbenzylcarbinyl acetate, heliotropyl acetate,eugenol acetate, isoeugenol acetate, phenylglycol diacetate,dimethylphenylcarbinyl acetate, phenylethylmethylethylcarbinyl acetate,veticol acetate, α-amylcinnamyl acetate, decahydro-β-naphthyl acetate,and furfuryl acetate.

The content of ingredient (B)(ii) is from 0.001 to 80 wt. %, preferablyfrom 1 to 80 wt. %, more preferably from 1.5 to 60 wt. % of thefragrance composition.

As ingredient (B)(iii), i.e., the lactones, lactones having total carbonnumbers of from 5 to 14, for example, compounds represented by thefollowing formula (3):

wherein R⁸ represents a hydrocarbon group having from 4 to 13 carbonatoms can be mentioned.

In formula (3), the hydrocarbon group represented by R⁸is a linear orbranched hydrocarbon group which may contain a cyclic hydrocarbon groupat least as a part thereof. Specifically, linear or branched alkylenegroups and alkenylene groups can be mentioned, and these alkylene groupsand alkenylene groups may each contain one or more aromatic rings.

Examples of the compounds of formula (3) include γ-butyrolactone,γ-valerolactone, angelic lactone, γ-hexalactone, γ-heptalactone,γ-octalactone, γ-nonalactone, 3-methyl-4-octanolide (whisky-lactone),γ-decalactone, γ-undecalactone, γ-dodecalactone, γ-jasmolactone(7-decenolactone), δ-hexalactone,4,6,6(4,4,6)-trimethyltetrahydropyran-2-one, δ-octalactone,δ-nonalactone, 2H-1-benzopyran-2-one, δ-decalactone, δ-2-decenolactone,δ-undecalactone, δ-dodecalactone, δ-tridecalactone, δ-tetradecalactone,lactoscatone, ε-decalactone, ε-dodecalactone, cyclohexyllactone,jasminlactone, cis-jasmonelactone, methyl-γ-decalactone,tetrahydro-6-(3-pentenyl)-2H-pyran-2-one, (E)-dec-8-en-5-olide(“JASMOLARITONE”, trade name of Firmenich, Inc.),tetrahydro-6-(3-hexenyl)-2H-pyran-2-one, (Z)-undec-8-en-5-olide(“JASMOLACTONE”, trade name of Bedoukian Research Inc.), menthalactone,and methyl dihydrojasmonate. Preferred are γ-octalactone, γ-nonalactone,γ-decalactone, γ-undecalactone, γ-dodecalactone, γ-jasmolactone(7-decenolactone), δ-octalactone, δ-nonalactone, 2H-1-benzopyran-2-one,δ-decalactone, δ-2-decenolactone, and δ-undecalactone.

The content of ingredient (B)(iii) is from 0.001 to 80 wt. %, preferablyfrom 0.001 to 60 wt. %, more preferably from 0.002 to 0 40 wt. % of thefragrance composition.

As ingredient (B)(iv), i.e., the ketone compounds having a cyclic orchain skeleton and having total carbon numbers of from 5 to 14, terpenylketones, aliphatic linear ketones and aliphatic cyclic ketones can bementioned.

Examples of the terpenyl ketones include camphor, carvone,dihydrocarvone, pulegone, menthone, piperitenone, diosphenol, fenchone,perpenone, geranylacetone, farnesylacetone, acetylcedrene (cedryl methylketone), oxocedrane (cedranone, cedrenone), acetylcaryophyllene,isolongifolanone (isolongifolane ketone), nootkatone, ionone,pseudoionone, methylionone, allylionone, irone, damascone, damascenone,isodamascone, 1-(3,3-dimethyl-6(1)-cyclohexen-1-yl)-pent-4-en-1-one(“DYNASCONE”), and trimethyl cyclohexenyl butenone (“IRITONE”, tradename of International Flavors & Fragrances Inc.). Preferred are ionone,damascone, damascenone, isodamascone, and1-(3,3-dimethyl-6(1)-cyclohexen-1-yl)-pent-4-en-1-one (“DYNASCONE”).

Examples of the aliphatic linear ketones include acetoin, diacetyl,methyl amyl ketone, ethyl amyl ketone, 2-pentanone, 3-hexanone,2-heptanone, 3-heptanone, 4-heptanone, 3-octanone, 2-nonanone,3-nonanone, 2-undecanone, methyl isopropyl ketone, methyl hexyl ketone,methyl nonyl ketone, methylheptenone, ethyl isoamyl ketone,2-tridecanone, mesityl oxide, butylidene acetone, methyl heptadienone,methyl heptenone, dimethyl octenone, methylene tetramethylheptanone(“KOAVONE”, trade name of International Flavors & Fragrances Inc.),5-hydroxy-4-octanone (butyroin), 3-hydroxymethyl-2-nonanone,2,3-pentanedione, 2,3-hexanedione, 3,4-hexanedione, 2,3-heptanedione,acetyl isovaleryl, 2-butyl-1,4-dioxaspiro[4.4]nonane (“JASMONE”, tradename of Henkel Corporation), and2,2,5,5-tetramethyl-4-isopropyl-1,3-dioxane.

Examples of the aliphatic cyclic ketones include amylcyclopentanone,amylcyclopentenone, 2-cyclopentylcyclopentanone, hexylcyclopentanone,butylcyclopentanone, maltol, ethyl maltol,2,5-dimethyl-4-hydroxyfranone, 4,5-dimethyl-3-hydroxy-5H-furan-2-one(“SUGARLACTONE”, trade name of Soda Aromatic Co., Ltd.),o-t-butylcyclohexanone, p-t-butylcyclohexanone, amylcyclopentanone,heptylcyclopentanone, dihydrojasmone, cis-jasmone, isojasmone,trimethylpentylcyclopentanone,3-methyl-5-(2,3,3-trimethyl-3-cyclopentenyl)-3-penten-2-o ne (“SANDEX”,trade name of Givaudan-Roure Corporation), cycloten,3,5-dimethyl-1,2-cyclopentadione, 3,4-dimethyl-1,2-cyclopentadione,3,3-dimethylcyclohexyl methyl ketone,1-acetyl-3,3-dimethyl-1-cyclohexene, 2-sec-butylcyclohexanone,3-methyl-5-propyl-2-cyclohexenone, cryptone, p-t-pentylcyclohexanone,2,3,5-trimethyl-4-cyclohexenyl-1-methyl ketone (“METHYL CYCLOCITRON”,trade name of International Flavors & Fragrances Inc.), nerone,4-cyclohexyl-4-methyl-2-pentanone, cyclohexenyl cyclohexanone,2,4-di-t-butylcyclohexanone (“CYCLOWOOD”, trade name of TakasagoInternational Corporation),3-methyl-4-(2,4,6-trimethyl-3-cyclohexenyl)-3-buten-2-one (“METHYLIRITONE”, trade name of International Flavors & Fragrances Inc.),allylionone, 2,6,6-trimethyl-2-cyclohexane-1,4-dione,2-acetyl-3,3-dimethylnorbornane,6-ethylideneoctahydro-5,8-methano-2H-1-benzopyran-2-one (“FLOREX”, tradename of International Flavors & Fragrances Inc.),4-methyltricyclo[6.2.1.02.7]undecan-5-one (“PLICATONE”, trade name ofFirmenich, Inc.), 6,7-dihydro-1,1,2,3,3,-pentamethyl-4(5H)-indanone(“CASHMERAN”, trade name of International Flavors & Fragrances Inc.),4(5)-acetyl-7,7,9-triemthylbicyclo[4.3.0]-1-nonene (“ATRINON”, tradename of Henkel Corporation), acetylisopropylmethylbicyclooctene,4-cyclohexyl-4-methyl-2-pentanone, p-menthen-6-ylpropanone (“NERONE”,trade name of Givaudan-Roure Corporation),2,2,5-trimethyl-5-pentylcyclopentanone,ethoxyvinyltetramethylcyclohexanone, dihydropentamethylindanone,7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-naphthalene (“ISO E SUPER”,trade name of International Flavors & Fragrances Inc.),2,6,7-trimethyl-1-acetyl-2,5,9-cyclododecatriene (“TRIMOFIX”, trade nameof International Flavors & Fragrances Inc.), acetylcedrene [ethanone,1-(2,3,4,7,8,8a-hexahydro-3,6,8,8-tetramethyl-1H-3a, 7-methanoazulen-5-yl)-]β-methylnaphthyl ketone.

Preferred is 7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-naphthalene(“ISO E SUPER”, trade name of International Flavors & Fragrances Inc.).

The content of ingredient (B)(iv) is from 0.001 to 80 wt. %, preferablyfrom 0.01 to 50 wt. %, more preferably from 0.1 to 30 wt. % of thefragrance composition.

As ingredient (B)(v), i.e., the aldehydes, aldehydes having total carbonnumbers of from 5 to 14, for example, compounds represented by thefollowing formula (4):R⁹—CHO  (4)wherein R⁹ represents a hydrocarbon group having from 4 to 13 carbonatoms and optionally containing an oxygen atom or nitrogen atom insertedin at least one carbon-carbon bond thereof can be mentioned.

The group represented by R⁹ can be a linear, branched or cyclichydrocarbon group, or a group containing a linear, branched or cyclichydrocarbon group with an oxygen atom or nitrogen atom inserted in atleast one carbon-to-carbon bond thereof. It is to be noted that the term“hydrocarbon group” as used herein includes both saturated andunsaturated ones and the term “cyclic hydrocarbon group” as used hereinincludes saturated, unsaturated and aromatic, cyclic hydrocarbon groups.As the atom inserted in the at least one carbon-to-carbon bond, anoxygen atom or a nitrogen atom can be mentioned, with an oxygen atombeing preferred. A preferred form of linkage with an oxygen atomcontained therein is an ether linkage in a linear ether or cyclic ether.

Preferred examples of R⁹ include alkyl groups, alkenyl groups, cyclichydrocarbon groups, cyclic hydrocarbyl-alkyl groups, cyclichydrocarbyl-alkenyl groups, aromatic hydrocarbon groups, aromatichydrocarbyl-alkyl groups, aromatic hydrocarbyl-alkenyl groups, andmonoterpene and other terpene groups.

Examples of ingredient (B)(v), i.e., the aldehydes include undecenal,heptanal, octanal, undecanal, dodecanal, 2-methylundecanal, citral,geranial, neral, citronellal, 3,7-dimethyloctanal (tetrahydrocitral),hydroxycitronellal, methoxycitronellal, α-methylenecitronellal(“BENGAMAL”, trade name of International Flavors & Fragrances Inc.),perilla aldehyde, methoxy dihydrocitronellal, citronellyloxyacetaldehyde, geranyloxy acetaldehyde, mirtenal, caryophyllene aldehyde,3-ethoxy-4-hydroxybenzaldehyde, and 4-hydroxy-3-methoxybenzaldehyde.Preferred are undecenal, heptanal, octanal, undecanal, dodecanal, and2-methylundecanal.

The content of ingredient (B)(v) is from 0.001 to 80 wt. %, preferablyfrom 0.01 to 70 wt. %, more preferably from 0.1 to 50 wt. % of thefragrance composition.

These ingredients (B) can be used either singly or in combination.Further, the content of ingredient (B) can preferably be from 0.001 to80 wt. % of the fragrance composition from the viewpoint of improvementsin scent and tastefulness.

Ingredient (C), i.e., the hydrocarbon having a total carbon number offrom 5 to 15 can be a terpenyl hydrocarbon. Illustrative are α-pinene,β-pinene, camphene, myrcene, dihydromyrcene, limonene, dipentene,terpinene, terpinolene, carene, allo-ocimene, ocimene, α-phellandrene,p-cymene, β-caryophyllene, β-farnesene, bisabolene, cedrene, cadinene,valencene, tsujopsene, da-i-ene, and longifolene. Preferred areα-pinene, β-pinene, and limonene.

These ingredients (C) can be used either singly or in combination,although it is preferred to use two or more of them. The content ofingredient (C) in the fragrance composition differs depending upon thekinds and combination of ingredients used, but can be preferably from0.001 to 90 wt. %, more preferably from 0.01 to 70 wt. %, even morepreferably from 0.1 to 40 wt. % from the standpoint of amount sufficientto mask an acid smell, ensuring abalance with other materials, andachieving improvements in scent and tastefulness.

From the standpoint of enhancing the scent emmited, making improvementsin the refreshing sensation and to give a more defined body for thefragrance, it is preferred to incorporate, in addition to theabove-described ingredients, a sulfur-containing compound as aningredient (D) in the fragrance composition according to the presentinvention. As the sulfur compounds, an organosulfur compound such as athiol compound, sulfide compound, disulfide compound, thioaldehydecompound or cyclic thioether compound can be mentioned. Specificexamples include propyl mercaptan, isopropyl mercaptan,2-methyl-3-buthanethiol, allyl mercaptan, isoamyl mercaptan,thiogeraniol, limonenethiol, 8-mercaptomenthone (sulfox), phenylmercaptan, o-thiocresol, 2-ethylthiophenol, 2-naphthylmercaptan,furfuryl mercaptan, 2-methyl-3-franthiol, dimethyl sulfide, dimethyldisulfide, dimethyl trisulfide, methylpropyl disulfide, methylpropyltrisulfide, propyl disulfide, dipropyl trisulfide, diallyl trisulfide,diallyl disulfide, dibutyl sulfide, methionol, 3-methylthio-1-hexanol,methional, mentho sulfide, dithiospirolactone, furfurylmethyl sulfide,2-methyl-5-methylthiofuran, methylfuryl disulfide, furfuryl disulfide,thiophene, tetrahydrothiophene, 3-thiophenecarboxaladehyde,5-methyl-2-thiophenecarboxaldehyde, tetrahydrothiophen-3-one,trithioacetone, 2-methyl-4-propyl-1,3-oxathiane, thioglycolic acid,methyl ethylthioacetate, ethyl methylthioacetate,2-methylmercaptopropionic acid, pineapple mercaptan, ethyl3-methylthiopropionate, ethyl thioacetate, furfuryl thioacetate,furfuryl thiopropionate, methyl thiobutyrate, methylmethanethiosulfonate, allyl isothiocyanate, benzyl isothianate, thialdine,2-methyl-4-propyl-1,3-oxathiane, p-menthane-8-thiol-3-one,p-mentene-8-thiol, and methyl β-methylthiopropionate.

From the standpoint of the amount sufficient to mask an acid smell andensuring a balance with other materials, the content of the sulfurcompound in the fragrance composition can be preferably from 0.00001 to1 wt. %, more preferably from 0.0001 to 0.5 wt. %, even more preferablyfrom 0.0002 to 0.4 wt. %.

The fragrance composition according to the present invention can alsocontain 1-(2-t-butylcyclohexyloxy)-2-butanol,dodecahydro-3a,6,6,9a-tetramethyl-naphtho[2.1-b]furan,2-ethoxynaphthalene, 2-methoxynaphthalene, 1H-3a,7-methanoazulene,octahydro-6-methoxy-3,6,8,8-tetramethyl-, [3R-(3α,3aβ,6β,7β,8aα)],2-oxybicyclo[2.2.2]octane, 1,3,3-trimethyl, 3,7,-dimethyl-2,6-octadienenitrile,4,4a,5,9b-tetrahydroindeno[1,2d]-1,3-dioxine,tetrahydro-4-methyl-2-(2-methyl-1-propenyl)-2H-pyran, cyclohexanol,3-(5,5,6-trimethylbicyclo[2.2.1]hept-2-yl)-cyclohexanol,2-tridecenenitrile, 2-methoxy-4-allylphenol,3-methyl-5-phenyl-1-pentanol, 1-(2-t-butylcyclohexyloxy)-2-butanol,and/or 2-methyl-4-(2,2,3-trimethyl-3-cyclopentene-1-yl)-2-buten-1-ol.From the viewpoint of imparting distinctiveness to the fragrance, thecontent of such an additional fragrant material may preferably be from0.001 to 50 wt. % of the fragrance composition.

In addition, the fragrance composition according to the presentinvention can also contain one or more of alcohols, polyhydric alcoholsand ethers.

Further, the present invention contains a fragrant material which isstable in acidic hair cosmetic compositions, especially acidic shampoos,and also contains a fragrant material which gives off a good scent fromfoam and also from a bottle mouth and has an excellent lasting scent.The fragrant materials included in ingredient (E) are each characterizedby the abundant release of scent from foam, the fragrant materialsincluded in ingredient (F) are each characterized by the abundantrelease of a scent from a bottle mouth, and the fragrant materialsincluded in ingredient (G) are each characterized by the goodpersistence of scent. A combination of fragrant materials selected asdesired from the ingredients (E), (F) and (G) makes it possible toobtain a well-balanced, excellent fragrance composition which is afragrance giving off a good scent from foam and from the bottle mouth,and the persistence of scent notes.

From the viewpoint of giving off a good scent upon application of a haircosmetic composition in which the fragrance composition according to thepresent invention is added, the content of ingredient (E) in thefragrance composition is from 10 wt. % to 70 wt. %, preferably from 10wt. % to 60 wt. %, more preferably from 15 wt. % to 60 wt. %. From theviewpoint of giving off a good scent from a bottle mouth, the content ofingredient (F) in the fragrance composition is from 5 wt. % to 60 wt. %,preferably from 5 wt. % to 55 wt. %, more preferably from 10 wt. % to 50wt. %. From the viewpoint of providing an excellent lasting scent, thecontent of ingredient (G) in the fragrance composition is from 10 wt. %to 70 wt. %, preferably from 10 to 60 wt. %, more preferably from 10 wt.% to 50 wt. %.

According to the present invention, a hair cosmetic composition can beformulated with the above-described fragrance composition containedtherein. As the fragrance composition according to the present inventionis excellent in long-term stability under high-temperature conditionsand can mask a smell peculiar to an acidic hair cosmetic composition, itis useful as a fragrance composition for acidic hair cosmeticcompositions, especially hair cosmetic compositions whose pHs arepreferably from 1 to 5, more preferably from 2 to 4 (even morepreferably, from3 to 4). The hair cosmetic compositions of pH 1 to 5according to the present invention can include hair cleansingcompositions, rinses, treatments, conditioning agents, hair packs, haircreams, styling hair care products, hair tonics, hair restorers, haircolognes and the like, each of which has a pH of from 1 to 5, butexcludes hair manicures, hair dyes, and permanent wave solutions. Amongthese, those used by washing them off, such as hair cleansingcompositions, e.g., shampoos and conditioning shampoos, and hair rinsesare preferred. It is to be noted that the term “hair cosmeticcomposition having a pH of 1 to 5” (25° C.) as used herein means a haircosmetic composition whose pH is from 1 to 5 when the undiluted haircosmetic composition is diluted 20-fold with water.

A hair cosmetic composition having a pH of 1 to 5 can be prepared with asimilar formula as an ordinary hair cosmetic composition except that itspH is controlled from 1 to 5. Accordingly, an oil ingredient, aconditioning agent, a humectant, a viscosity increasing agent, aviscosity controlling agent, an emulsifier, a colorant, a stabilizer, anultraviolet absorber, a preservative, a pH adjuster and the like areadded as needed in addition to one or more surfactants as a cleansingingredient. As the surfactants, anionic surfactants, nonionicsurfactants, and amphoteric surfactants can be mentioned. Examples ofthe anionic surfactants include polyoxyethylene alkyl ether sulfates,polyoxyethylene alkenyl ether sulfates, alkyl sulfates, andpolyoxyalkylene alkyl phenyl ether sulfates, especially sulfate-typeanionic surfactants such as polyoxyethylene alkyl ether sulfates andalkyl sulfates; and sulfonates and carboxylates such as alkylsulfosuccinate salts, polyoxyalkylene alkyl sulfosuccinate salts, higherfatty acid salts, and alkane sulfonate salts.

Examples of the nonionic surfactants include polyoxyalkylene sorbitanfatty acid esters, polyoxyalkylene sorbitol fatty acid esters,polyoxyalkylene glycerol fatty acid esters, polyoxyalkylene fatty acidesters, polyoxyalkylene alkyl ethers, polyoxyalkylene alkyl phenylethers, polyoxyalkylene (hydrogenated) castor oils, sucrose fatty acidesters, triglycerin alkyl ethers, polyglycerin fatty acid esters, fattyacid alkanolamides, and alkyl glycosides. Among these, preferred arealkyl glycosides, polyoxyalkylene (C₈-C₂₀) fatty acid esters,polyoxyethylene sorbitan fatty acid esters, polyoxyethylene hydrogenatedcastor oil, and fatty acid alkanolamides. As the fatty acidalkanolamides, those having from 8 to 18 carbon atoms, especially thosecontaining acyl groups of from 10 to 16 carbon atoms are preferred. Asthe fatty acid alkanolamides, either monoalkanolamides ordialkanolamides are usable, and those containing a hydroxyalkyl group offrom 2 to 3 carbon atoms are preferred. Examples include oleicdiethanolamide, palm kernel fatty acid diethanolamide, coconut fattyacid diethanolamide, lauric diethanolamide, polyoxyethylene coconutfatty acid monoethanolamide, coconut fatty acid monoethanolamide, lauricisopropanolamide, and lauric monoethanolamide.

As the amphoteric surfactants, betaine-type surfactants can bementioned. Among these, more preferred are betainealkyldimethylaminoacetates and fatty acid amidopropylbetaines, withfatty acid amidopropylbetaines being preferred. As the fatty acidamidopropylbetaines, those having 8 to 18 carbon atoms, especially thosecontaining acyl groups of from 10 to 16 carbon atoms are preferred, withlaurylamidopropyl betaine, palm kernel fatty acid amidopropyl betaineand cocamidopropyl betaine being preferred.

The surfactant can be contained preferably at from 1 to 50 wt. %, morepreferably at from 8 to 30 wt. %, even more preferably at from 10 to 22wt. % in the hair cosmetic composition.

As the cationic surfactants, mono(long-chain alkyl) quaternary ammoniumsalts are preferred. Specific examples include cetyltrimethylammoniumchloride, stearyltrimethylammonium chloride, aralkyltrimethylammoniumchloride, and behenyltrimethylammonium chloride, withbehenyltrimethylammonium chloride being preferred. Further, the cationicsurfactants can also include those formed by adding tertiary amines andthe below-described organic salts.

As the oil ingredients, higher alcohols, lanolins, liquid paraffin,higher fatty acids, ester oils, and silicones can be mentioned. Examplesof the silicones can include the following silicones:

(1) Dimethylpolysiloxanes

Those represented by the following formula can be mentioned as examples.(Me)₃Si—[(Me)₂SiO]_(d)—Si(Me)₃wherein Me represents a methyl group, and d stands for a value of from 3to 20,000.

(2) Amino-modified Silicones

Preferred examples are those having an average molecular weight of fromabout 3,000 to 100,000 and described under the name of amodimethiconesin the third edition of the CTFA Cosmetic Ingredient Dictionary, U.S.A.,although various amino-modified silicones are usable. Preferably, theseamino-modified silicones are used as aqueous emulsions. As commercialproducts, “SM8704C” (product of Dow Corning Toray Silicone Co., Ltd.)and “DC929” (product of Dow Corning Corporation) can be mentioned.

(3) Other Silicones

In addition to the above-described silicones, polyether-modifiedsilicones, methylphenylpolysiloxane, fatty-acid-modified silicones,alcohol-modified silicones, alkoxy-modified silicones, epoxy-modifiedsilicones, fluorine-modified silicones, cyclic silicones, andalkyl-modified silicones can also be mentioned.

The oil ingredient can be contained preferably at from 0.05 to 10 wt. %,more preferably at from 0.1 to 5 wt. %, even more preferably at from 0.3to 2 wt. % in the hair cosmetic composition.

As the conditioning agent, a cationic polymer is preferred. Examples ofthe cationic polymer include cationized cellulose derivatives, cationicstarch, cationized guar gum derivatives, homopolymers ofdiallyl(quaternary ammonium) salts, diallyl(quaternary ammonium)salt/acrylamide copolymer, quaternized polyvinylpyrrolidone derivatives,polyglycol-polyamine condensation products, vinylimidazoliumtrichloride/vinylpyrrolidone copolymer,hydroxyethylcellulose/dimethyldiallylammonium chloride copolymer,vinylpyrrolidone/quaternized dimethylaminoethyl methacrylate copolymer,polyvinylpyrrolidone/alkyl aminoacrylate copolymers,polyvinylpyrrolidone/alkyl aminoacrylate/vinylcaprolactam copolymer,vinylpyrrolidone/methacrylamidopropyl-trimethylammonium chloridecopolymer, alkylacrylamide/acrylate/alkylaminoalkylacrylamide/polyethylene glycol methacrylate copolymers, adipicacid/dimethylaminohydroxypropyl ethylenetriamine copolymer(“CARTARETIN”, product of Sandoz, Inc., U.S.A.), and cationic polymersdisclosed in JP-A-53-139734 or JP-A-60-36407. Preferred examples arecationized cellulose derivatives and cationized guar gum derivatives.The conditioning agent can be contained preferably at from 0.05 to 5 wt.%, more preferably at from 0.1 to 3 wt. %, even more preferably at form0.3 to 1 wt. % in the hair cosmetic composition.

In the hair cosmetic composition according to the present invention, anorganic acid can be additionally incorporated to make improvements inthe finish of hair such as sleekness and style. Examples of the organicacid include carboxylic acids such as monocarboxylic acids, dicarboxylicacids, hydroxycarboxylic acids and polycarboxylic acids, andalkylphosphoric acids. Among these, carboxylic acids, especiallydicarboxylic acids and hydroxycarboxylic acids are preferred. Examplesof the dicarboxylic acids include malonic acid, succinic acid, glutaricacid, adipic acid, maleic acid, fumaric acid, and phthalic acid, andillustrative of the hydroxycarboxylic acids are glycolic acid, lacticacid, hydroxyacrylic acid, oxybutyric acid, glyceric acid, malic acid,tartaric acid, and citric acid. Among these, α-hydroxycarboxylic acids,especially lactic acid and malic acid are preferred.

Two or more of these organic acids can be used in combination. Further,the content of the organic acid can be preferably from 0.05 to 10 wt. %,more preferably from 0.1 to 5 wt. %, even more preferably from 0.5 to 1wt. % of the hair cosmetic composition according to the presentinvention.

In the hair cosmetic composition according to the present invention, anaromatic alcohol may be additionally incorporated to make improvementsin touch feel and post-shampoo sleekness. Examples of the aromaticalcohol include benzyl alcohol, benzyloxyethanol and phenoxyethanol,with benzyl alcohol and benzyloxyethanol being preferred.

Two or more of these aromatic alcohols can be used in combination.Further, the content of the aromatic alcohol can be preferably from 0.01to 20 wt. %, more preferably from 0.1 to 10 wt. %, even more preferablyfrom 0.5 to 5 wt. % of the hair cosmetic composition according to thepresent invention.

The hair cosmetic composition having a pH of 1 to 5 according to thepresent invention can be produced ina similar manner as conventionalhair cosmetic compositions except that its pH is controlled from 1 to 5.

EXAMPLES

In the Examples, “%” means “wt. %”, and “part” or “parts” means “part byweight” or “parts by weight”.

Example A Conditioning Shampoos

An unfragranced conditioning shampoo (pH 3.7) of the formula shown inTable 1 was prepared. Aliquots of the unfragranced conditioning shampoowere fragranced with 0.5 wt. % of the fragrance compositions 1 to 12shown in Table 2 and Table 3, respectively, to formulate conditioningshampoos. Samples of the conditioning shampoos were weighed as much as20 g each in standard 50-mL wide-mouth bottles “PS-06” (made of clearglass), and were placed in a storage cabinet controlled at 50° C. Onemonth later, a scent given off from the surface of each shampoo wasranked by two expert panelists in accordance with the below-describedranking standard, and the average of their ranking scores was recorded.The ranking was an overall ranking on a masking effect for an acidsmell, stability and the like while taking into consideration thespreading characteristics, the floating pattern and the like of thefragrance.

Ranking Standard:

5: Excellent

4: Good

3: Satisfactory as a commercial product

2: Slightly poor

1: Poor TABLE 1 Conditioning shampoo composition (pH 3.7) (wt. %) SodiumPOE(2) lauryl ether sulfate 11.0 Sodium lauryl sulfate 5.0 Cationizedguar gum 0.3 Malic acid 0.75 Lactic acid 0.1 Sodium chloride 0.2 Benzylalcohol 0.5 Cocoyl monoethanolamide 1.0 Dimethicone (viscosity: 100,000cps) 0.5 Amodimethicone 0.1 Myristyl alcohol 1.0 Cetanol 0.5 Ethyleneglycol distearate 3.0 Cationized hydroxyethylcellulose 0.3 Glycerol 1.0Sodium hydroxide q.s. to pH 3.7 Deionized water Balance

TABLE 2 Fragrance compositions Types Ingredient names 1 2 3 4 5 6 7 A:MUSK Musk ketone 0 3 3 3 3 3 3 A: MUSK “GALAXOLIDE” 0 93 93 93 93 93 93B-i: ESTER Cis-3-hexenyl salicylate 0 0 15 0 0 15 15 B-i: ESTER Ethyl2-methylbutyrate (DPG 10%) 0 0 5 0 0 5 5 B-i: ESTER “FRUITATE” (ethyltricyclodecanylcarboxylate) 0 0 5 0 0 5 5 B-i: ESTER Tricyclodecenylpropionate 0 0 20 0 0 20 20 B-i: ESTER Methyl salicylate (DPG 10%) 0 0 50 0 5 5 B-ii: ESTER o-t-Butyl cyclohexylacetate 0 0 15 0 0 15 15 B-iii:KETONE “ADMASCENONE” 0 0 0 0.5 0 0 0.5 B-iii: KETONE “α-DAMASCONE” 0 0 01.5 0 0 1.5 B-iii: KETONE β-Ionone 0 0 0 20 0 0 20 B-iii: KETONEMethylionone-G 0 0 0 25 0 0 25 C: TERPENE Limonene 0 0 0 0 25 25 25SOLVENT Dipropylene glycol 350 244 191 207 229 164 117 FORMULA*^(note 1)650 650 650 650 650 650 650 Total (parts by weight) 1000 1000 1000 10001000 1000 1000FORMULA*^(note 1) Fragrance formula formed primarily of alcohols andcontaining aldehydes, dipropylene glycol, etc.

TABLE 3 Fragrance compositions Types Ingredient names 8 9 10 11 12 —Hexyl acetate 5 0 0 0 0 — Iso-amyl acetate 2 0 0 0 0 — Indole (DPG 10%)5 0 0 0 0 A Musk ketone 3 0 3 3 3 A “GALAXOLIDE” 185 0 185 185 185 B-i“FRUITATE” 0 0 0 5 5 B-i Tricyclodecenyl propionate 0 0 0 20 20 B-iMethyl salicylate (DPG 10%) 0 0 0 5 5 B-i Cis-3-hexenyl salicylate 0 0 015 15 B-i Ethyl 2-methylbutyrate (DPG 10%) 0 0 0 5 5 B-ii o-t-Butylcyclohexylacetate 0 0 0 15 15 B-iii G-Decanolactone 0 20 0 20 20 B-iv“DAMASCENONE” 0.5 0 0 0.5 0.5 B-iv “d-DAMASCONE” 1.5 0 0 1.5 1.5 B-ivβ-Ionon 20 0 0 20 20 B-iv Methylionon-G 25 0 0 25 25 B-vα-Methyl-1,3-benzodioxol-5-propanal 0 0 10 10 10 B-v Decanal (DPG 10%) 00 2 2 2 B-v Dodecanal (DPG 10%) 0 0 1 1 1 B-v Hexylcinnamic aldehyde 0 090 90 90 B-v α-Methyl-4-(1-methylethyl)-benzenepropanal 0 0 15 15 15 B-vp-t-Butyl-α-methylhydrocinnamic aldehyde 0 0 140 140 140 C Limonene 25 00 25 25 D p-Menthane-8-thiol-3-one (1% DPG) 0 0 0 0 1 EtherDodecahydro-3a,6,6,9a-tetramethyl-naphtho[2.1-b]furan 0 0 0 0 0.3FORMULA*^(note 2) 340 340 340 340 340 Solvent Dipropylene glycol 388 640402 57 55.7 Total (parts by weight) 1000 1000 1000 1000 1000FORMULA*^(note 2) Fragrance formula formed primarily of alcohols andcontaining solvents such as dipropylene glycol, etc.

TABLE 4 Results of Ranking in Stability and Masking Effect Comp. Exs.Examples Comp. Exs. Examples 1 2 1 2 3 4 5 3 4 6 7 8 Composition ofTable 1 99.50% 99.50% 99.50% 99.50% 99.50% 99.50% 99.50% 99.50% 99.50%99.50% 99.50% 99.50% Fragrance composition 1 0.50% Fragrance composition2 0.50% Fragrance composition 3 0.50% Fragrance composition 4 0.50%Fragrance composition 5 0.50% Fragrance composition 6 0.50% Fragrancecomposition 7 0.50% Fragrance composition 8 0.50% Fragrance composition9 0.50% Fragrance composition 10 0.50% Fragrance composition 11 0.50%Fragrance composition 12 0.50% changes Room temp. 1 day 1 3 3.5 4 3.5 45 4 2 4 5 5 with 50° C. 1 month later <1 2 3 4 3.5 3.5 4.5 1 2 3.5 4.54.5< time Performance 1 3 3.5 4 3.5 4 5 4 2 4 5 5 (masking performance)

As shown in FIG. 4, the conditioning shampoos formulated by fragrancingthe aliquots of the unfragranced conditioning shampoo of Table 1 withthe fragrance compositions of Examples 1 to 8 according to the presentinvention were acknowledged to have clear advantages in changes withtime and performance (masking performance) over the conditioningshampoos formulated by fragrancing the aliquots of the unfragrancedconditioning shampoo of Table 1 with the fragrance compositions ofComparative Examples 1 to 4 from a comparison therebetween.

In the case of Example 2, for example, the change with time upon elapsedtime of 1 month at 50° C. were ranked “4” (good) like the change withtime one day after the formulation owing to the inclusion of thefragrance composition 4 according to the present invention, therebydemonstrating excellent stability at high temperatures. In the case ofExample 5, the change with time upon elapsed time of 1 month at 50° C.were ranked “4.5” as compared with “5” one day after the formulationowing to the inclusion of the fragrance composition 7 according to thepresent invention, there by also demonstrating excellent stability athigh temperatures.

Example B Clear Shampoo

(wt. %) Sodium POE(2) lauryl ether sulfate 10.0 Myristyl alcohol 0.5Cationized hydroxyethylcellulose 0.2 Laurylamidopropyl betaine 0.5Cocoyl monoethanolamide 0.3 Malic acid 0.75 Glycerol 1.0 Deionized waterBalance

A clear shampoo formulated by adding the fragrance composition 7 to theabove-described composition (pH 3.7) such that its content became 0.5wt. % was free of any acid smell, and retained the fragrance over a longtime.

Example C Anti-Dandruff Shampoo

(wt. %) Sodium POE(2) lauryl ether sulfate 10.0 Sodium lauryl sulfate5.5 Myristyl alcohol 1.0 Cetanol 0.5 Cationized hydroxyethylcellulose0.3 Cationized guar gum 0.3 Cocoyl monoethanolamide 0.5 Dimethicone(polymerization degree: 2,000) 0.5 Dimethicone (polymerization degree:200) 0.5 Malic acid 0.7 Benzyloxyethanol 0.5 Ethylene glycol distearate3.0 Cocoyl benzalconium chloride 0.5 Glycerol 1.0 Sodium chloride 0.2Deionized water Balance

A shampoo formulated by adding the fragrance composition 7 to theabove-described composition (pH 3.7) such that its content became 0.5wt. % was free of any acid smell, and retained the fragrance over a longtime.

Example D Conditioner

(wt. %) Lactic acid 4 Polypropylene glycol (m.w. 400) 1Behenyltrimethylammonium chloride 1.7 Stearyltrimethylammonium chlorideBehenyl alcohol 5.1 Methylpolysiloxane (“SH500-5000CS”) 3 Isopropylpalmitate 1 Dipentaerythritol fatty acid ester 0.1 Benzyloxyethanol 0.3Hydroxyethylcellulose 0.2 Polyethylene glycol (m.w. 100,000) 48% Sodiumhydroxide 0.2 Deionized water Balance

A conditioner formulated by adding the fragrance composition 7 to theabove-described composition (pH 3.3) such that its content became 0.5wt. % was free of any acid smell, and retained the fragrance over a longtime.

Example E

With respect to each fragrant material, ranking was conducted inaccordance with the ranking methods and ranking standards to bedescribed hereinafter.

<Ranking Methods & Ranking Standards>

a. Scent from Foam

(1) Ranking Method

1. Each fragrant material (0.5 g) was added to a shampoo base (99.5 g)to fragrance the shampoo base (0.5 wt. %).

2. On the following day, 0.5 g of the thus-fragranced shampoo base wasweighed in a 100-cc container, and water was then added to produce atotal weight of 10 g so that a 5% aqueous solution was obtained.

3. The aqueous solution was lathered for 1 minute with a commercialelectric beater.

4. A scent given off from the foam was ranked in accordance with thefollowing standard.

(1) Ranking Standard

-   -   5: A scent is given off very well so that the smell of the        cosmetic base (acid smell) is completely masked.    -   4: A scent is given off well so that the smell of the cosmetic        base (acid smell) is masked well.    -   3: A scent is given off well, but the masking of the smell of        the cosmetic base (acid smell) is a little insufficient.    -   2: A scent is given off, but the smell of the cosmetic base        (acid smell) is also recognized.    -   1: A scent is poorly given off, and the smell of the cosmetic        base (acid smell) is recognized.        b. Scent from the Bottle Mouth (1) Ranking Method

1. Each fragrant material (0.5 g) was added to a shampoo base (99.5 g)to fragrance the shampoo base (0.5 wt. %).

2. The thus-formulated shampoo was poured in 20 g aliquots into glassbottles of 50 g capacity (standardized wide-mouth bottles “PS-06”, madeof clear glass), followed by capping the glass bottles.

3. On the following day, each bottle was uncapped to rank a scent fromthe bottle mouth.

(2) Ranking Standard

-   -   5: A scent is given off very well so that the smell of the        cosmetic base (acid smell) is completely masked.    -   4: A scent is given off well so that the smell of the cosmetic        base (acid smell) is masked well.    -   3: A scent is given off well, but the masking of the smell of        the cosmetic base (acid smell) is a little insufficient.    -   2: A scent is given off, but the smell of the cosmetic base        (acid smell) is also recognized.    -   1: A scent is poorly given off, and the smell of the cosmetic        base (acid smell) is recognized.        c. Persistence of Scent

(1) Ranking Method

1. Each fragrant material (0.5 g) was added to a shampoo base (99.5 g)to fragrance the shampoo base (0.5 wt. %).

2. On the following day, 2.5 g of the thus-formulated, fragranced samplewere applied to a tress of false hair.

3. The tress of false hair was washed for 1 minute and rinsed (withrunning water) for 1 minute, and was then lightly dried with a towel.

4. The tress of false hair was allowed to dry naturally, and one daylater, the scent was ranked.

(2) Ranking Standard

-   -   5: A scent remains very well so that the smell of the cosmetic        base is masked sufficiently.    -   4: A scent remains well so that the smell of the cosmetic base        is masked sufficiently.    -   3: A scent remains, but the masking of the smell of the cosmetic        base is a little insufficient.    -   2: A scent remains only faintly so that the masking of the smell        of the cosmetic base is insufficient.    -   1: No scent remains at all.        d. Changes in Odor with Time (Stability)

(1) Ranking Method

Each fragrant material was added to an acidic shampoo base. Samples werestored for 1 month in constant-temperature chambers controlled at 0° C.and 50° C., respectively. After the temperatures of the respectivesamples were allowed to return to room temperature one month later, ascent from the sample stored at 50° C. was ranked in comparison with ascent from the sample stored at 0° C. in accordance with thebelow-described standard. The scent emitted from the sample stored at 0°C. was taken as standard. The ranking was performed by a panel of 3 to 6experts, and the average of their scores was indicated with 0.5increments.

(2) Ranking Standard

-   -   5: Substantially the same in both odor quality and intensity        compared with the standard (the sample stored at 0° C.).    -   4: Slightly changed in both odor quality and intensity compared        with the standard, but still good as a scent of merchandise.    -   3: Changed in both odor quality and intensity compared with the        standard, but still acceptable practically as a scent of        merchandise.    -   2: Obviously changed in both odor quality and intensity compared        with the standard.    -   1: Pronouncedly changed in both odor quality and intensity        compared with the standard.        <Ranking Results>

Tables 5 to 13 show fragrant materials which were found to have goodstability and also to be good in any of the properties of scent fromfoam, scent from a bottle mouth and the persistence of a scent, based onthe results of the above-described rankings. TABLE 5 Scent from Scentbottle from Persistence of Names of fragrant materials Stability mouthfoam scent Ingredient α-Amylcinnamic aldehyde 4.5 4.0 4.0 3.0 EAcetophenone 4.5 5.0 4.0 4.0 E Decanal 5.0 4.0 5.0 2.5 E Undecanal 5.04.0 4.5 2.5 E Undecenal 5.0 4.5 5.0 2.5 E Dodecanal 5.0 4.0 5.0 2.5 E2-Methylundecanal 4.5 4.0 4.5 2.5 E Octanal 5.0 4.5 4.5 2.5 E Nonanal5.0 4.5 4.5 2.5 E Allylcyclohexyl propionate 0.0 0.0 0.0 0.0 E Allylphenoxyacetate 0.0 0.0 0.0 0.0 E Allylphenoxyacetatic acid 3.5 4.5 4.04.0 Anisaldehyde 3.5 4.0 4.0 2.5 E Anisyl acetate 3.5 3.5 3.5 3.5 EAnisyl acetone 4.0 3.5 4.0 4.0 E Borneol 4.0 4.5 4.5 2.0 E3-(p-Tert-butylphenyl)-propanal (“BOURGENAL”, 4.0 4.0 4.5 2.5 E tradename of Quest) 7-Methyl-3,5-dihydro-2H-benzodioxepin-3-one 3.0 5.0 5.03.5 E (“CALONE”, trade name of Pfizer) Cinnamyl acetate 3.5 4.0 4.0 4.0E Cis-4-decenal 4.5 5.0 5.0 2.5 E Cis-jasmone 3.5 3.0 3.5 3.0 E

TABLE 6 Persistence Scent from Scent of Names of fragrant materialsStability bottle mouth from foam scent Ingredient Citronellyloxyacetaldehyde 4.0 4.0 4.5 2.5 E Dodecanenitrile (“CLONAL”, trade name ofIFF) 4.0 4.5 4.5 3.5 E 2-Methyl-3-(isopropylphenyl)-propanal (cyclamenaldehyde) 3.5 3.5 4.0 2.0 E Dihydrojasmone 3.5 4.0 4.5 3.0 E Methyldihydrojasmonate 4.5 3.5 3.5 2.0 E Dihydromircenol 3.0 4.0 4.0 2.0 ETricyclodecylidene-4-butanal (“DUPICAL”, trade name of Quest) 4.0 4.55.0 2.0 E Ethyl 2-cyclohexylpropionate (“ETHYL POIRENATE”, trade name ofKao) 4.0 4.5 4.0 4.0 E Ethyl2,6,6-trimethyl-1,3-cyclohexadiene-1-carboxylate (“ETHYL 4.0 4.5 4.5 4.0E SUFRANATE”, trade name of Quest) Ethyl isovalerate 3.5 4.0 4.0 1.0 EEthyl linalol 3.0 2.5 3.0 2.0 E Ethyl vanillin 3.5 4.5 5.0 2.0 E Eugenol4.5 4.0 4.0 3.5 E 6-Ethylidenoctahydro-5,8-methano-1H-1-benzopyran-2-one(“FLOREX”, 4.0 4.0 4.5 2.5 E trade name of Firmenich) Ethyltricyclodecan-2-yl-carboxylate (“FRUITATE”, trade name of Kao) 5.0 3.54.0 3.5 E Franeol 4.0 5.0 5.0 1.5 EEthyl-3-(bicyclo[2.2.1]hepto-5-en-2-yl)-3-methyl glycidate 3.0 3.5 4.04.0 (“GLYCOMEL”, trade name of Firmenich)2-Methyl-3-(3,4-methylenedioxyphenyl)-propanol (“HELIONAL”, trade 3.54.0 4.5 3.0 E name of IFF) Cis-3-hexenyl methylcarbonate (“LIFFAROME”,trade name of IFF) 2.0 3.0 4.0 2.5 E2-Methyl-3-(4-tert-butylphenyl)-propanal (“LILIAL”, Givaudan) 3.5 3.54.0 2.0 E Linalol 3.5 4.0 4.0 3.54(3)-(4-Hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde 2.5 2.54.0 2.5 E (“LYRAL”, trade name of IFF) Methyl anthranilate 4.0 4.5 4.54.0 E Methyl β-naphthyl ketone 4.5 4.0 4.5 4.5 E4(3)-(4-Methyl-3-pentenyl)-3-cyclohexene-1-carboxaldehyde (“MYRAC 4.04.5 5.0 2.5 E ALDEHYDE”, trade name of IFF)

TABLE 7 Scent from Scent Persistence of Names of fragrant materialsStability bottle mouth from foam scent Ingredient2-(2-(4-Methyl-3-cyclohexen-1-yl)propyl)cyclopentanone 4.5 4.0 4.5 4.0 E(“NECTARYL”, trade mark of Givaudan) Nookkatone 3.5 3.5 3.5 3.0 EPhenylacetaldehyde 1.0 4.5 5.0 2.5 E 2-Cyclohexylpropanal (“POLLENALII”, trade name of Kao) 4.5 4.0 4.0 2.0 E8-Methoxytricyclodecane-4-carboxaldehyde (“SCENTENAL”, trade 4.0 4.0 5.03.0 E name of Firmenich) Thymol 4.5 4.5 4.5 2.0 E Trans-2-decenal 4.55.0 5.0 2.5 E Trans-2-hexanal 4.5 4.5 5.0 2.5 E Tricyclodecenyl acetate4.0 3.0 4.0 4.0 E Tricyclodecenyl propionate 4.0 3.5 4.0 4.0 E1-Acetyl-2,6,10-trimethylcyclododeca-2,5,9-triene 4.0 2.5 3.0 3.0 E(“TRIMOFIX”, trade name of IIF) Vanillin 3.5 4.5 4.5 2.5 E 1-Octen-3-ylacetate 3.5 4.0 3.0 2.0 F 2,5-Decadienal 3.0 4.5 4.5 2.5 F2,4-Octadienal 3.0 5.0 4.0 2.5 F 2,6-Nonadienal 3.0 5.0 5.0 2.5 F1,3-Oxathiane 2-methyl-4-propionate 3.0 4.0 2.5 2.0 F 2-Methylbutyl2-methylbutyrate 3.0 4.0 1.0 2.0 F 2-Methylbutyl isovalerate 3.5 4.0 1.52.5 F 2-Methylbutyl valerate 3.0 3.5 1.5 2.0 F Acetophenone 4.0 5.0 3.53.5 F Acetylcedrene [ethanone, 4.0 3.5 3.0 4.5 F1-(2,3,4,7,8,8a-hexahydro-3,6,8,8-tetramethyl-1H-3a,7-methanoazulen-5-yl)-]β-methylnaphthyl ketone α-Damascon 4.0 4.0 4.5 3.0 F Hexanol 4.54.0 1.5 2.5 F Hexanal 5.0 5.0 4.0 2.5 F

TABLE 8 Scent from Scent Persistence of Names of fragrant materialsStability bottle mouth from foam scent Ingredient Heptanal 5.0 4.5 4.02.5 F Allylionone 3.5 4.5 3.5 3.0 F Allyl heptanoate 3.0 3.5 3.0 1.5 FAllyl hexanoate 3.0 4.5 1.5 1.5 F α-Pinene 3.0 3.0 2.5 1.0 F α-Terpinene3.0 4.5 3.0 1.0 F β-Damascon 4.0 3.0 3.5 3.0 F Benzaldehyde 4.5 4.5 2.02.0 F Benzyl acetate 3.0 4.5 4.0 3.0 F Benzyl propionate 3.0 4.0 3.5 3.0F Camphor 4.0 4.5 2.0 2.0 F2-Methyl-3-(para-methoxyphenyl)-propylaldehyde (“CANTHOXAL”, 3.0 3.5 2.52.0 F trade name of IFF) Cedrene 4.0 4.5 2.0 4.0 F3-Proylbicyclo(2.2.1)hept-5-ene-2-carbaldehyde 4.0 5.0 4.5 3.5 F(“CHRYSANTHAL”, trade name of Quest) Cinnamic alcohol 4.5 4.0 3.5 2.5 FCis-3-hexenol 4.5 4.5 4.5 3.0 F Cis-3-hexenyl propionate 3.0 5.0 3.0 2.0F Cis-jasmone 3.5 3.5 3.5 3.0 F Citral 4.5 4.5 4.0 2.5 F Citronellal 4.04.5 3.0 2.5 F Citronellol 3.0 3.5 3.5 2.5 F Citronellyl nitrile 4.5 4.53.0 4.0 F Thiol addition product of limonene (for example, “CORPS 4.04.0 2.5 2.0 F PAMPLEMOUSSE”, trade name of Prodasynth) Methylcyclopentylidenacetate 3.5 4.5 1.0 2.0 F Dimethlbenzylcarbinyl acetate4.0 3.5 3.5 3.5 F

TABLE 9 Scent from Scent Persistence of Names of fragrant materialsStability bottle mouth from foam scent Ingredient1-(2,6,6-Trimethyl-1,3-cyclohexadien-1-yl)-2-buten-1-one 4.0 4.5 4.0 3.0F (“DAMASCENONE”, trade name of Firmenich)1-(2,6,6-Trimethyl-3-cyclohexen-1-yl)-2-buten-1-one 4.0 4.5 4.5 3.0 F(“DELTA-DAMASCONE”, trade name of IFF) Dihydrojasmone 3.5 4.5 4.0 3.5 FEthyl maltol 4.0 5.0 4.5 1.5 F Ethyl trimethylhexanoate 4.0 3.0 0.5 1.5F Ethyl 2-methylbutylate 3.0 4.0 1.0 1.0 F Ethyl butyrate 3.0 4.5 3.51.0 F Ethyl heptanoate 4.0 3.5 1.0 1.0 F Ethyl hexanoate 4.0 4.5 1.5 1.0F Ethyl nonanoate 4.0 3.5 1.5 1.0 F Ethyl octanoate 4.0 3.0 1.5 1.0 FEthyl propionate 2.5 5.0 2.0 1.0 F Ethyl valerate 3.0 4.5 3.5 1.0 FFenchone 4.0 5.0 2.5 3.0 F p-Ethyl-2,2-dimethylhydrocinnamaldehyde(“FLORALOZONE”, trade 3.0 4.5 4.0 2.5 F name of IFF) Ethyl2-tert-butylcyclohexylcarbonate (“FLORAMAT”, trade name 4.0 4.0 2.5 3.5F of Kao) 2-sec-Butylcyclohexanone (“FRESCOMENTHE”, trade name of 4.03.5 2.5 2.5 F Givaudan) Ethyl-2-methyl-1,3-dioxolan-2-acetate 3.5 3.01.0 3.0 F Geraniol 4.0 3.5 3.5 2.5 F Geranyl nitrile 4.5 5.0 4.0 4.5 F3-Methyl-5-prop-2-cyclohexen-1-one (“GRAVENONE”, trade name of 3.5 4.02.5 2.0 F Dragoco) Hexylcinnamic aldehyde 3.0 3.5 3.5 3.0 F Heptylcyclopentanone 4.0 4.0 4.5 4.0 F Iron 4.5 4.5 3.0 2.0 F Isobutylsalicylate 4.0 3.5 2.5 3.5 F

TABLE 10 Scent Persis- from Scent tence Names of bottle from of fragrantmaterials Stability mouth foam scent Ingredient 1-(2,4,4-Trimethyl- 4.04.0 3.0 3.0 F 2-cyclohexen- 1-yl)-2-buten-1-one (“ISO-DAMASCONE”, tradename of Dragoco) L-Carvone 4.0 5.0 4.5 2.0 F 3,7-Dimethyl-2(3), 4.0 4.53.5 4.5 F 6-nonadienenitrile (“LEMONILE”, trade name of Givaudan)Limonene 4.5 3.5 2.0 1.0 F L-Menthol 4.0 3.0 2.5 2.0 F Menthone 4.0 5.03.5 2.0 F Maltol 4.0 4.5 4.0 1.0 F 3-Methyl-5- 4.0 4.0 3.5 2.5 Fphenylpentanal (“MEFRANAL”, trade name of Quest) Methyl benzoate 3.5 4.52.0 3.0 F Methyl butyrate 3.0 4.5 1.0 1.0 F Methyl dihydrojasmonate 3.54.0 2.0 4.0 F Methyl geranylate 4.0 3.0 1.5 2.0 F Methyl octanoate 4.04.0 1.5 2.0 F Methyl salicylate 4.0 4.5 3.5 2.0 F Methyl valerate 4.05.0 3.0 1.0 F Butyl butyrate 4.0 3.5 1.0 1.0 F Hexyl acetate 3.5 4.0 1.51.0 F Hexylcyclopentanone 4.0 3.5 3.5 3.0 F Amyl valerate 4.0 3.5 1.51.5 F Amyl butyrate 3.5 4.0 1.0 1.0 F Amyl propionate 3.0 4.5 2.0 1.0 FOrthomethoxycinnamic 2.5 4.0 4.0 2.0 F aldehyde o-Tert-butylcyclohexyl4.0 3.5 2.0 3.0 F acetate Para-Amylcyclohexanone 4.0 3.5 2.5 3.0 FParacymene 4.0 4.5 1.5 1.0 F

TABLE 11 Scent from Scent Persistence of Names of fragrant materialsStability bottle mouth from foam scent Ingredient Phenylethyl alcohol4.0 3.5 3.0 2.5 F Phenylethyl propionate 3.0 4.0 3.5 2.5 F Phenylhexanol4.5 2.5 2.0 2.5 F Phenylpropyl acetate 3.0 3.5 3.0 3.0 F4-Methyltricyclo[6.2.1.02.7]undecan-5-one (“PLICATONE”, trade 3.0 3.02.5 2.5 F name of Firmenich) p-Menthane-8-thiol-3-one 4.0 5.0 4.5 2.5 Fp-Tert-butylcyclohexyl acetate 4.0 3.5 2.0 3.5 F Styrallyl acetate 3.55.0 3.0 3.0 F Terpineol 4.0 3.5 2.0 2.0 F Terpinolene 3.0 3.5 1.5 1.5 FTerpinyl propionate 3.0 3.5 2.0 2.5 F Trans-2-hexanal 3.0 4.5 3.0 2.5 FTrans-2-hexenyl acetate 3.5 3.5 1.5 1.5 F Trimethylhexanal 4.5 4.5 3.52.5 F 2,4-Dimethyl-3-cyclohexenylcarboxaldehyde (“TRIPLAL”, trade 4.55.0 4.5 2.5 F name of IFF) 2,2,5-Trimethyl-5-pentylcyclopentanone(“VELOUTONE”, trade 4.0 3.5 2.0 2.5 F name of Firmenich)4-Cyclohexyl-4-methyl-2-pentanone (“VETIVERTONE”, trade name of 3.5 4.02.5 3.0 F Quest) Vetiveryl acetate 3.5 4.0 3.5 3.5 F Amylcyclopentane4.0 4.5 4.0 3.0 F Allyl anthranillate, 3.5 2.5 2.5 4.0 G1-(2-Tert-butylcyclohexyloxy)-2-butanol (“AMBER CORE”, trade 4.0 3.5 3.04.0 G name of Kao) 7-cyclohexadecenolide (ambrettolide) 2.5 2.5 3.5 4.0G (3α,6,6,9α-tetramethyldodecahydronaphtho[2.1-b]furan 4.5 3.5 3.5 4.0 G(“AMBROXANE”, trade name of Kao)

TABLE 12 Scent from Scent Persistence of Names of fragrant materialsStability bottle mouth from foam scent Ingredient2-Ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol 4.0 2.5 3.54.5 G (“BACDANOL”, trade name of IFF; “BANGALOL”, trade name ofGivaudan) Benzophenone 5.0 3.0 3.5 4.0 G Benzyl alcohol 4.5 4.0 3.5 4.0G Caryophyllene 4.0 1.5 1.0 3.5 G6,7-Dihydro-1,1,2,3,3,-pentamethyl-4(5H)-indanone 5.0 4.5 4.5 4.0 G(“CASHMERAN”, trade name of IFF) 4-acetyl-6-tert-butyl-1,2-dimethylindan(“CELESTOLIDE”, trade 5.0 2.0 2.5 3.5 G name of International Flavors &Fragrances Inc.) Cis-3-hexenyl anthranylate 3.0 2.0 2.0 4.0 G 4-Hexenylsalicylate 3.0 3.0 2.5 3.5 G Coumarin 4.0 3.5 4.0 4.0 GCyclopentadecanone 5.0 2.5 2.5 4.0 G Dynascone 4.0 4.5 5.0 3.5 G3-Methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten-2-o 4.0 4.0 4.04.0 G 1 (“EVANOL”, trade name of Givaudan) Ethyl salicylate 3.5 3.5 1.54.0 G Eugenol acetate 3.0 3.0 3.0 3.5 G Geranyl cyclopentanone 5.0 3.53.5 4.0 G Oxacyclohexadecen-2-one (“HABANOLIDE”, trade name ofFirmenich) 2.5 2.0 2.5 4.0 G Heliotropine 4.5 4.0 4.0 4.0 G Heliotropylacetone 4.0 2.5 2.0 4.0 G Hexadecanolide 2.5 2.0 2.5 4.0 G α-Ionone 4.54.0 4.0 4.0 G β-Ionone 4.5 3.0 2.5 4.5 G7-Acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethylnaphthalene 4.53.0 3.5 5.0 G (“ISO E SUPER”, trade name of IFF)

TABLE 13 Scent from Scent Persistence of Names of fragrant materialsStability bottle mouth from foam scent Ingredient Isobutyl anthranylate3.0 2.0 2.5 4.0 G Isoeugenol acetate 3.0 2.5 2.0 3.5 G δ-Decalactone 4.03.5 3.5 4.5 G α-Methylionone 4.5 3.0 3.0 4.0 G γ-Methylionone 4.5 3.53.5 4.5 G 3-Methylcyclopentadecenone (“MUSCENONE DELTA”, trade name of5.0 3.5 4.0 4.5 G Firmenich) 3-Methylcyclopentadecanone (muscone) 4.02.5 3.0 4.0 G Ethylene dodecanedioate (“MUSK C-14”, trade name ofTakasago) 2.5 2.0 2.0 4.0 G Musk ketone 5.0 4.5 4.5 5.0 G11-Oxa-16-hexadecanolide (“MUSK R-1”, trade name of Quest) 2.5 3.0 3.54.0 G 5-Cyclohexadecen-1-one (“MUSK TM-II”, trade name of Soda) 4.0 2.52.5 3.5 G Butyl anthranylate 3.0 2.0 2.5 4.0 G Hexyl salicylate 3.0 2.02.5 4.0 G Amyl salicylate 3.5 2.5 2.0 4.0 G 10-Oxa-16-hexadecanolide(“OXALIDE”, trade name of Takasago) 2.5 2.0 2.0 3.5 G4,6,6,7,8,8-Hexamethyl-1,3,4,6,7,8-hexahydrocyclopentabenzopyran 4.0 3.03.0 5.0 G (“PEARLIDE PURE”, trade name of Kao) Cyclopentadecanolide(“PENTALIDE”, trade name of Soda) 2.5 2.0 2.0 4.0 G2-Cyclohexylidene-2-phenyl acetonitrile (“PEONILE”, trade name 4.5 3.53.5 4.5 G of Givaudan)3,3-Dimethyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten- 4.0 3.03.5 4.0 G 2-ol (“POLYSANTOL”, trade name of Firmenich)4-(Parahydroxyphenyl)-2-butanone (“RASPBERRY KETONE”, trade 4.5 4.5 4.54.5 G name of Takasago)2-Methyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol 4.5 3.5 4.04.0 G (“SANDALMYSORE CORE”, trade name of Kao)3-Methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-pentan-2-ol 4.0 2.5 3.04.0 G (“SANDALORE”, trade name of Givaudan) Cis-8-cyclohexadecenolide(“SCENTOLIDE”, trade name of Synarom) 4.0 2.0 2.0 4.0 G6-Acetyl-1,1,2,4,4,7-hexatetralin (“TONALIDE”, trade name of 5.0 2.5 3.55.0 G PFW)

Example F

The formula of a fragrance composition for an acidic shampoo will beshown. TABLE 14 Fragrance Composition for Acidic Shampoo Fragrancecompositions Ingredient names 13 14 15 16 17 18 19 Ingredient E DecanalE 0.2 0.2 0.2 — 0.2 — — Dihydromircenol E 20.0 20.0 20.0 — 20.0 — —“CALONE” E 0.3 0.3 0.3 — 0.3 — — “HELIONAL” E 10.0 10.0 10.0 — 10.0 — —“FRUITATE” E 5.0 5.0 5.0 — 5.0 — — Tricyclodecenyl propionate E 20.020.0 20.0 — 20.0 — — Eugenol E 20.0 20.0 20.0 — 20.0 — — Methylanthranylate E 0.1 0.1 0.1 — 0.1 — — Cyclamen aldehyde E 15.0 15.0 15.0— 15.0 — — “LILIAL” E 140.0 140.0 140.0 — 140.0 — — Anisyl acetone E20.0 20.0 20.0 — 20.0 — — Vanillin E 2.0 2.0 2.0 — 2.0 — — Total ofingedient E 252.6 252.6 252.6 0.0 252.6 0.0 0.0 Ingredient F “TRIPLAL” F1.5 1.5 — 1.5 — 1.5 — Methyl salicylate F 0.5 0.5 — 0.5 — 0.5 —Citronellole F 25.0 25.0 — 25.0 — 25.0 — “δ-DAMASCONE” F 1.5 1.5 — 1.5 —1.5 — “DAMASCENONE” F 0.5 0.5 — 0.5 — 0.5 — Phenylethyl alcohol F 60.060.0 — 60.0 — 60.0 — Hexylcinnamic aldehyde F 90.0 90.0 — 90.0 — 90.0 —Acetylcedrene F 25.0 25.0 — 25.0 — 25.0 — “CORPS PAMPLEMOUSSE 10% LIM” F0.2 0.2 — 0.2 — 0.2 — Styrallyl acetate F 0.0 0.0 — 0.0 — 0.0 — Ethyl2-methylbutyrate F 0.5 0.5 — 0.5 — 0.5 — o-Tert-butylcyclohexyl acetateF 15.0 15.0 — 15.0 — 15.0 — Terpineol F 15.0 15.0 — 15.0 — 15.0 — Totalof ingedient F 234.7 234.7 0.0 234.7 0.0 234.7 0.0 Ingredient Gδ-Decalactone G 20.0 — 20.0 20.0 — — 20.0 Ionon G 20.0 — 20.0 20.0 — —20.0 γ-Methylionone G 25.0 — 25.0 25.0 — — 25.0 “SANDALMYSORE CORE” G18.0 — 18.0 18.0 — — 18.0 “AMBROXANE 10%” G 0.3 — 0.3 0.3 — — 0.3Heliotropine G 35.0 — 35.0 35.0 — — 35.0 Musk ketone G 3.0 — 3.0 3.0 — —3.0 “PEARLIDE PURE” G 185.0 — 185.0 185.0 — — 185.0 Total of ingedient G306.3 0.0 306.3 306.3 0.0 0.0 306.3 Other ingredients 206.4 512.7 441.1459.0 747.4 765.3 693.7 TOTAL 1000.0 1000.0 1000.0 1000.0 1000.0 1000.01000.0

The fragrance compositions 13 to 19 shown in Table 14 were added at 0.5%to aliquots of the acidic shampoo base of Table 1 to fragrance the same.The thus-formulated shampoos were then ranked. The ranking results areshown in Table 15. TABLE 15 Acidic Shampoo Examples Comparative Examples9 10 11 12 3 4 5 Composition of Table 1 99.50% 99.50% 99.50% 99.50%99.50% 99.50% 99.50% Fragrance composition 13  0.50% Fragrancecomposition 14  0.50% Fragrance composition 15  0.50% Fragrancecomposition 16  0.50% Fragrance composition 17  0.50% Fragrancecomposition 18  0.50% Fragrance composition 19  0.50% TOTAL 100.0%100.0% 100.0% 100.0% 100.0% 100.0% 100.0% Ranking of scent Scent fromfoam 5.0 4.0 4.0 3.0 3.5 2.5 2.0 Scent from bottle mouth 5.0 4.0 3.5 4.02.0 3.0 3.0 Persistence of scent 5.0 3.0 4.5 4.0 2.0 2.5 3.0 Overallranking of scent 5.0 4.0 4.0 3.5 2.0 2.0 2.5 Changes in scent with time(50° C./1 month) 5.0 4.0 5.0 4.0 4.0 4.0 4.0<Results>

Example 9 making the combined use of all three types of ingredients wasfound to give off a good scent in all stages, to keep the acid smell ofthe cosmetic base masked, and to have an excellent fragrance as a finalproduct. Examples 10 to 12 each making the combined use of two types ofingredients from the ingredients (E), (F) and (G) were each found inmasking and balance to give off a good scent in all the stages, to keepthe acid smell of the cosmetic base masked, and to have an excellentfragrance as a final product. In contrast, each of Comparative Examples3 to 5 which made the use of only one type of ingredient (E), (F) or (G)was not balanced well in scent in each of the stages, and even by anoverall judgement, was found to have an insufficient fragrance as afragrance of a final product.

<Overall Ranking>

A standard for the ranking item “overall ranking of fragrance” inExamples F and G will now be shown.

The “overall ranking of fragrance” is a ranking determined by takinginto comprehensive consideration the three ranking items of a scent fromfoam, a scent from a bottle mouth and the persistence of a scent, andthe following ranking standard is relied upon.

-   -   5: A well-balanced scent is given off very well in all the        stages, and the smell of a cosmetic base is completely masked.    -   4: A well-balanced scent is given off very well in all the        stages, and the smell of a cosmetic base is masked well.    -   3: A well-balanced scent is given off very well in all the        stages, and the smell of a cosmetic base is substantially        masked.    -   2: A scent is poorly given off in at least one of the stages,        and the masking of the smell of a cosmetic base is insufficient.    -   1: A scent is poorly given off in all the stages, and the        masking of the smell of a cosmetic base is insufficient.

Example G

The formula of a fragrance composition for an acidic shampoo will beshown. TABLE 16 Fragrance Composition for Acidic Shampoo Fragrancecompositions Ingredient names 20 21 22 23 24 25 26 Ingre-dient E“LILIAL” E 70 70 70 — 70 — — Ethyl linalol E 40 40 40 — 40 — — “CALONE”10% E 5 5 5 — 5 — — Total of ingedient E 115 115 115 0 115 0 0Ingredient F “DAMASCENONE” 50% F 2 2 — 2 — 2 — “TRIPLAL” F 2 2 — 2 — 2 —Citronellole F 100 100 — 100 — 100 — Hexylcinnamic aldehyde F 50 50 — 50— 50 — Methyl hydrojasmonate F 200 200 — 200 — 200 — Limonene F 30 30 —30 — 30 — o-Tert-butylcyclohexyl acetate F 60 60 — 60 — 60 — Total ofingedient F 444 444 0 444 0 444 0 Ingre-dient F “SANDALMYSORE CORE” G 60— 60 60 — — 60 “ISO E SUPER” G 100 — 100 100 — — 100 “HABANOLIDE” G 100— 100 100 — — 100 “PEARLIDE PURE” G 150 — 150 150 — — 150 Total ofingedient G 410 0 410 410 0 0 410 Other ingredients 31 441 475 146 885556 590 TOTAL 1000 1000 1000 1000 1000 1000 1000

The fragrance compositions 20 to 26 shown in Table 16 were added at 0.5%to aliquots of the acidic shampoo base of Table 1 to fragrance the same.The thus-formulated shampoos were then ranked. The ranking results areshown in Table 17. TABLE 17 Acidic Shampoo Examples Comparative Examples13 14 15 16 6 7 8 Composition of Table 1 99.50% 99.50% 99.50% 99.50%99.50% 99.50% 99.50% Fragrance composition 20  0.50% Fragrancecomposition 21  0.50% Fragrance composition 22  0.50% Fragrancecomposition 23  0.50% Fragrance composition 24  0.50% Fragrancecomposition 25  0.50% Fragrance composition 26  0.50% TOTAL 100.0%100.0% 100.0% 100.0% 100.0% 100.0% 100.0% Ranking of scent Scent fromfoam 5.0 4.0 4.0 3.0 3.0 2.5 2.0 Scent from bottle mouth 5.0 4.0 3.5 4.03.0 3.0 2.0 Persistence of scent 5.0 3.0 4.5 4.0 2.0 2.0 3.0 Overallranking of scent 5.0 4.0 4.0 3.5 2.0 2.5 2.5 Changes in scent with time(50° C./1 month) 5.0 4.0 5.0 5.0 4.0 4.0 4.0<Results>

Example 13 making the combined use of all the three types of ingredientswas found to give off a good scent in all the stages, to keep the acidsmell of the cosmetic base masked, and to have an excellent fragrance asa final product. Examples 14 to 16 each making the combineduse of twotypes of ingredients from the ingredients (E), (F) and (G) were eachfound in masking and balance to give off a good scent in all the stages,to keep the acid smell of the cosmetic base masked, and to have anexcellent fragrance as a final product. In contrast, each of ComparativeExamples 6 to 8 which made the use of only one type of ingredient (E),(F) or (G) was not balanced well in scent in each of the stages, andeven by an overall judgement, was found to have an insufficientfragrance as a fragrance of a final product.

Industrial Applicability

The fragrance compositions according to the present invention areexcellent inmasking effects for a smell peculiar to hair cosmeticcompositions having a pH of 1 to 5, and are also superb in long-termstability under high-temperature conditions. Acidic hair cosmeticcompositions with the fragrance compositions added therein can eachretain a good scent over a long period.

A well-balanced addition of the ingredients (E) to (G) to a fragrancecomposition makes it possible to obtain a fragrance composition for ahair cosmetic composition having a pH of 1 to 5, which can stably retaina good scent in the hair cosmetic composition having a pH of 1 to 5,gives off a good scent upon application of the hair cosmeticcomposition, is excellent in the persistence of scent after theapplication, and moreover, gives off a good scent in a bottled state(from a bottle mouth).

1. A fragrance composition to be added to a hair cosmetic compositionhaving a pH of 1 to 5, comprising the following ingredients (A) and (B),or (A) and (C), or (A), (B) and (C): (A) from 0.1 to 70 wt. % of a musk;(B) from 0.001 to 80 wt. % of at least one compound selected from thefollowing compounds (i) to (v): (i) compounds represented by thefollowing formula(1):R¹—COOR²  (1) wherein R¹ represents a linear, branched or cyclichydrocarbon group having from 2 to 14 carbon atoms, which may contain anoxygen atom or nitrogen atom in at least one carbon-to-carbon bondthereof, and R² represents a linear, branched or cyclic hydrocarbongroup having from 1 to 15 carbon atoms, which may contain an oxygen atomor nitrogen atom in at least one carbon-to-carbon bond thereof, (ii)compounds represented by the following formula (2):R³—COOR⁴  (2) wherein R³ represents a hydrogen atom or methyl group, andR⁴ represents a hydrocarbon group or cyclic hydrocarbon group, in whichan α-carbon or β-carbon to an ether linkage in an ester group in formula(2) has a branched chain, (iii) lactones having total carbon numbers offrom 5 to 14, (iv) ketone compounds having a cyclic or chain skeletonand having total carbon numbers of from 5 to 14, (v) aldehydes havingtotal carbon numbers of from 5 to 14; and (C) from 0.01 to 90 wt. % of ahydrocarbon having a total carbon number of from 5 to
 15. 2. Thefragrance composition according to claim 1, further comprising, asingredient (D), from 0.00001 to 1 wt. % of a sulfur-containing compound.3. A fragrance composition for a hair cosmetic composition having a pHof 1 to 5, comprising at least two ingredients selected from thefollowing ingredients (E), (F) and (G), wherein a content of saidingredient (E) is from 10 wt. % to 70 wt. % of said fragrancecomposition, a content of said ingredient (F) is from 5 wt. % to 60 wt.% of said fragrance composition, and a content of said ingredient (G) isfrom 10 wt. % to 60 wt. % of said fragrance composition: (E) at leastone ingredient selected from α-amylcynnamic aldehyde, acetophenone,decanal, undecanal, undecenal, dodecanal, 2-methylundecanal, octanal,nonanal, allylcyclohexyl propionate, allyl phenoxyacetate, anisaldehyde,anisyl acetate, anisyl acetone, borneol,3-(p-tert-butylphenyl)-propanal,7-methyl-3,5-dihydro-2H-benzodioxepin-3-one, cinnamyl acetate,cis-4-decenal, cis-jasmone, citronellyloxy acetaldehyde,dodecanenitrile, 2-methyl-3-(isopropylphenyl)-propanal (cyclamenaldehyde), dihydrojasmone, methyl dihydrojasmonate, dihydromircenol,tricyclodecylidene-4-butanal, ethyl 2-cyclohexylpropionate, ethyl2,6,6-trimethyl-1,3-cyclohexadiene-1-carboxylate, ethyl isovalerate,ethyl linalol, ethyl vanillin, eugenol,6-ethylidenoctahydro-5,8-methano-1H-1-benzopyran-2-one, ethyltricyclodecan-2-yl-carboxylate, franeol,ethyl-3-(bicyclo[2.2.1]hepto-5-en-2-yl)-3-methyl glycidate,2-methyl-3-(3,4-methylenedioxyphenyl)-propanol, cis-3-hexenylmethylcarbonate, 2-methyl-3-(4-tert-butylphenyl)-propanal,4(3)-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxald ehyde, methylanthranilate, methyl β-naphthyl ketone,4(3)-(4-methyl-3-pentenyl)-3-cyclohexene-1-carboxaldehyde,2-(2-(4-methyl-3-cyclohexen-1-yl)propyl)cyclopentanone, nookkatone,phenylacetaldehyde, 2-cyclohexylpropanal,8-methoxytricyclodecane-4-carboxaldehyde, thymol, trans-2-decenal,trans-2-hexanal, tricyclodecenyl acetate, tricyclodecenyl propionate,1-acetyl-2,6,10-trimethylcyclododeca-2,5,9-triene, and vanillin; (F) atleast one ingredient selected from 1-octen-3-yl acetate, 2,5-decadienal,2,4-octadienal, 2,6-nonadienal, 1,3-oxathiane 2-methyl-4-propionate,2-methylbutyl 2-methylbutyrate, 2-methylbutyl 2-isovalerate,2-methylbutyl valerate, acetophenone, acetylcedrene [ethanone,1-(2,3,4,7,8,8a-hexahydro-3,6,8,8-tetramethyl-1H-3a,7-methanoazulen-5-yl)-]β-methylnaphthyl ketone, α-damascon, hexanol, hexanal,heptanal, allylionone, allyl heptanoate, allyl hexanoate, α-pinene,α-terpinene, β-damascon, benzaldehyde, benzyl acetate, benzylpropionate, camphor, 2-methyl-3-(para-methoxyphenyl)-propylaldehyde,cedrene, 3-proylbicyclo(2.2.1)hept-5-ene-2-carbaldehyde, cinnamicalcohol, cis-3-hexenol, cis-3-hexenyl propionate, cis-jasmone, citral,citronellal, citronellol, citronellyl nitrile, thiol addition product oflimonene, thiol substitution product of limonene, methylcyclopentylidenacetate, dimethlbenzylcarbinyl acetate,1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-2-buten-1-one,1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-2-buten-1-one, dihydrojasmone,ethyl maltol, ethyl trimethylhexanoate ethyl 2-methylbutylate, ethylbutyrate, ethyl heptanoate, ethyl hexanoate, ethyl nonanoate, ethyloctanoate, ethyl propionate, ethyl valerate, fenchone,p-ethyl-2,2-dimethylhydrocinnamaldehyde, ethyl2-tert-butylcyclohexylcarbonate, 2-sec-butylcyclohexanone,ethyl-2-methyl-1,3-dioxolan-2-acetate, geraniol, geranyl nitrile,3-methyl-5-prop-2-cyclohexen-1-one, hexylcinnamic aldehyde, heptylcyclopentanone, iron, isobutyl salicylate,1-(2,4,4-trimethyl-2-cyclohexen-1-yl)-2-buten-1-one, L-carvone,3,7-dimethyl-2(3),6-nonadienenitrile, limonene, L-menthol, menthone,maltol, 3-methyl-5-phenylpentanal, methyl dihydrojasmonate, methylbenzoate, methyl butyrate, methyl geranylate, methyl octanoate, methylsalicylate, methyl valerate, butyl butyrate, hexyl acetate,hexylcyclopentanone, amyl valerate, amyl butyrate, amyl propionate,orthomethoxycinnamic aldehyde, o-tert-butylcyclohexyl acetate,para-amylcyclohexanone, paracymene, phenylethyl alcohol, phenylethylpropionate, phenylhexanol, phenylpropyl acetate,4-methyltricyclo[6.2.1.02.7]undecan-5-one, p-menthane-8-thiol-3-one,p-tert-butylcyclohexyl acetate, styrallyl acetate, terpineol,terpinolene, terpinyl propionate, trans-2-hexanal, trans-2-hexenylacetate, trimethylhexanal, 2,4-dimethyl-3-cyclohexenylcarboxaldehyde,2,2,5-trimethyl-5-pentylcyclopentanone, and4-cyclohexyl-4-methyl-2-pentanone, (G) allyl anthranillate,1-(2-tert-butylcyclohexyloxy)-2-butanol, 7-cyclohexadecenolide(ambrettolide), (3α,6,6,9α-tetramethyldodecahydronaphtho[2.1-b]furan,2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol,benzophenone, benzyl alcohol, caryophyllene,6,7-dihydro-1,1,2,3,3,-pentamethyl-4(5H)-indanone,4-acetyl-6-tert-butyl-1,1-dimethylindan, cis-3-hexenyl anthranylate,4-hexenyl salicylate, coumarin, cyclopentadecanone, dynascone,3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten-2-ol, ethylsalicylate, eugenol acetate, geranyl cyclopentanone,oxacyclohexadecen-2-one, heliotropine, heliotropyl acetone,hexadecanolide, α-ionone, β-ionone,7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl naphthalene,isobutyl anthranylate, isoeugenol acetate, δ-decalactone,α-methylionone, γ-methylionone, 3-methylcyclopentadecenone,3-methylcyclopentadecanone (muscone), ethylene dodecanedioate, muskketone, 11-oxa-16-hexadecanolide, 5-cyclohexadecen-1-one, butylanthranylate, hexyl salicylate, amyl salicylate,10-oxa-16-hexadecanolide,4,6,6,7,8,8-hexamethyl-1,3,4,6,7,8-hexahydrocyclopenta benzopyran,6-acetyl-1,1,2,4,4,7-hexatetralin, cis-8-cyclohexadecenolide,3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-pentan-2-ol,2-methyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol-2-butanone,3,3-dimethyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-pen ten-2-ol,2-cyclohexylidene-2-phenyl acetonitrile, and cyclopentadecanolide.
 4. Afragrance composition for a hair cosmetic composition having a pH of 1to 5, comprising said ingredients (E), (F) and (G) as defined in claim3.
 5. The fragrance composition according to claim 4 for a hair cosmeticcomposition having a pH of 1 to 5, wherein a content of said ingredient(E) is from 10 wt. % to 70 wt. % of said fragrance composition, acontent of said ingredient (F) is from 5 wt. % to 60 wt. % of saidfragrance composition, and a content of said ingredient (G) is from 10wt. % to 60 wt. % of said fragrance composition.
 6. The hair cosmeticcomposition having a pH of 1 to 5, comprising a fragrance compositionaccording to any one of claims 1 to 5.